Compendium of Organic Synthetic Methods
Compendium of Organic Synthetic Methods Volume 11 MICHAEL B. SMITH
DEPARTMENT OF CHEMISTRY THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT
A JOHN WILEY & SONS, INC., PUBLICATION
Cover illustration was adapted from “DisconnectBy the Numbers: A Beginner’s Guide to Synthesis” by M.B. Smith. Journal of Chemical Education, 1990,67,848-856.
Copyright 02003 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, elcetronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, h e . , 111 River Street, Hobokcn, NJ 07030, (201) 748-601 I , fax (201) 748-6008, e-mail:
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ISBN 0-471-25965-9 Printed in the United States of America. 10 9 8 7 6 5 4 3 2 1
CONTENTS PREFACE ABBREVIATIONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
PREPARATION OF ALKYNES PREPARATION OF ACID DERIVATIVES AND ANHYDRIDES PREPARATION OF ALCOHOLS PREPARATION OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENES AND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS PREPARATION OF HALIDES AND SULFONATES PREPARATION OF HYDRIDES PREPARATION OF KETONES PREPARATION OF NITRILES PREPARATION OF ALKENES PREPARATION OF OXIDES PREPARATION OF DIFUNCTIONAL COMPOUNDS
AUTHOR INDEX
vii ix xiii xiv xv 1 9 18 90 115 226 264 310 335 366 377 386 417 425 470 4.83
709
V
PREFACE
Since the original volume in this series by Ian and Shuyen Harrison, the goal of the Compendium of Organic Synthetic Methods was to facilitate the search for functional group transformations in the original literature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Volume 3 of the series. Wade became the author for Volume 4 and continued with Volume 5. I began editing the series with Volume 6, where I introduced an author index for the first time and added a new chapter (Chapter 15, Oxides). Volume 7 introduced Sections 378 (Oxides - Alkynes) through Section 390 (Oxides - Oxides). This volume introduces Section 74G (Cyclobutanations). The Compendium is a handy desktop reference that will remain a valuable tool to the working Organic chemist, allowing a “quick check” of the literature. It also allows one to ”browse” for new reactions and transformations that may be of interest. The number of articles that comprise Organic literature is very large, and the Compendium is a focused and highly representative review of the literature and is offered in that context. Compendium of Organic Synthetic Methods, Volume 1 1 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1999, 2000 and 2001. The classification schemes used for Volumes 6-1 0 have been continued,- but one new section was added. Section 74G (Cyclobutanations) describes methods that produce cyclobutane rings. As in the past, difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special instructions for the use of Volume 11. Author citations and the Author Index have been continued as in Volumes 6-10. Every effort has been made to keep the manuscript error free. Where there are errors, I take full responsibility. If there are questions or comments, the reader is encouraged to contact me directly at the address, phone, fax, or Email addresses given below. As I have throughout my writing career, I thank my wife Sarah and my son Steven, who have shown unfailing patience and devotion during this work. Steven Smith also prepared many of the drawings used in this volume, and I thank him for that contribution. I also thank Dr. Darla Henderson and Amy Romano, the editors for this volume. Michael B. Smith Department of Chemistry University of Connecticut 55 N. Eagleville Road Storrs, Connecticut 06269-3060 vii
viii
PREFACE
Voice phone: (860) 486-2881 F a : (860) 486-2981 Email:
[email protected] Homepage: http://orgchem.chem.uconn.edu/home/mbs-home. html Storrs, Connecticut April, 2003
ABBREVIATIONS
Ac acac AlBN aq.
Acetyl Acety lacetonate am-bis-i sobutyronitri le Aqueous 9-Borabicyclo[3.3.1 ]nonylboryl
9-BBN BER BINAP Brnim Bn
BZ
9-Borabicyclo[3.3. llnonane Borohydride exchange resin 2R.3S-2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl 1-butyl-3-methylimidaolium benzyl benzoyl
BOC
1-Butoxycarbonyl
bpy @PY) Bu CAM CAN cat.
2,2'-Bipyridyl n-Butyl Carboxamidomethyl Ceric ammonium nitrate cycloCatalytic
Cbz
Carbobenzyloxy
Chirald COD COT CP CSA CTAB
2S,3R-(+)-4-dimethylamino1,2-diphenyl-3-methylbutan-2-ol I ,5-Cyclooctadienyl 1,3,5-~yclooctatrienyl Cyclopentadienyl Camphorsulfonic acid cetyltrimethylammonium bromide C16H33NMe3+Br
CY(c-C&~i)
Cyclohexyl
C-
O C
DABCO dba DBE DBN DBU DCC DCE DCM DDY
0
Temperature in Degrees Centigrade 1,4-Diazabicylco[2.2.2]octane dibenzylidene acetone 1,2-Dibrornoethane 1,8-Diazabicyclo[5.4.O]undec-7-ene 1,5-Diazabicycl0[4.3 .O]non-5-ene
1,3-Dicyclohexylcarbodiimide
1,2-Dichloroethane dichloromethane 2,3-Dichloro-5,6-dicyano1,4-benzoquinone
+Ol8"
0 $OCH2Ph
BrCH2CH2Br
c-C~HI~-N=C=N-C-C~H II CICH2CH2C1 CHzC12
ix
ABBREVIATIONS
X
% de DEA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DMA DME
% Diasteromeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride 1,2-bis-(Dipheny1phosphino)ethane 1,4-bis-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dimethylacetamide Dimethoxyethane
DMF
N,N‘-Dimethylfonnamide
h P
bis-[1,3-Di@-methoxypheny1)-1,3-propanedionato] dipivaloylmethanato 1,4-bis-(DiphenyIphosphino)butane Ph,P(CH,)dPPh, 1,2-bis-(Dipheny1phosphino)ethane PhZPCH,CH,PPh,
dPm dPPb dPPe dPPf dPPP dvb e% ee
EE Et EDA EDTA Emim FMN fod
FP
FVP Grubbs’ catalyst
MeOCH2CH20Me
il
H
N(CH3)Z
his-(Dipheny1phosphino)ferrocene 1,3-bis-(Diphenylphosphino)propane Ph,P(CH,),PPh, Divinylbenzene Electrolysis % Enantiomeric excess 1 -Ethoxyethoxy EtO(Me)CHOEthyl -CH2CH3 Ethy lenediamine HZNCH2CHzNHZ Ethylenediaminetetraacetic acid 1-ethyl-3-methylimidazolium Flavin mononucleotide fris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate Cyclopentadienyl-bis-carbonyliron Flash Vacuum Pyrolysis CI~(PC~,),RU=CHP~
n
MesGrubbs’ catalyst 11
HN(CH2CH3)2 EtO2C-N=NCOzEt (Me2CHCH2),AIH Ph,PCHZCHzPPh, Ph2P(CH&PPh,
NvN. Mes
I Ru = CHPh CI. I
“”
E Y 3
h hv
1 ,S-HD HMPA HMPT iPr LlCA (LIPCA) LDA LHMDS LTMP MABR
hour (hours) Irradiation with light 1,5-Hexadienyl Hexamethylphosphoramide (Me,N),P=O Hexamethylphosphorus triamide (Me2N)3P Isopropyl -CH(CH3)2 Lithium cyclohexylisopropylamide Lithium diisopropylamide LiN(iPr), Lithium hexamethyl disilazide LiN(SiMe,), Lithium 2,2,6,6-tetramethylpiperidide Methylaluminum bis-(4-bromo-2,6-di-tert-butylphenoxide)
ABBREVIATIONS MAD mCPBA Me MEM Mes MOM Ms MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) NMP Oxone
bis-(2,6-di-r-butyl-4-methylphenoxy)methyl aluminum mefa-Chloroperoxybenzoic acid Methyl -CH3 P-Methoxyethoxymethyl MeOCH2CH20CH2Mesityl 2,4,6-tri-Me-C6H2 Methox ymethyl MeOCH,Methanesulfonyl CH3S02Molecular Sieves (3A or 4A) Methylthiomethyl CH3SCHZNicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Naphthyl (C10H8) Norbornadiene N-Bromosuccinimide N-C hlorosuccinimide N-Iodosuccinimide Raney nickel N-Methyl-2-pyrrolidinone 2 KHSO,.KHS04.K,S04 Polymeric backbone
PCC PDC PEG
Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol
Ph
Phenyl
PhH PhMe Phth pic
Benzene Toluene Phthaloyl 2-Pyridinecarboxylate
Pip
Piperidino
PMP Pr
4-methoxypheny l n-Propyl
PY
Pyridine
quant. Red-A1 sBu sBuLi Siamyl TADDOL TASF TBAB TBAF TBAI TBDMS TBHP (1-BuOOH)
Quantitative yield [(MeOCH2CH20)2A1H2]Na sec-Butyl CH,CH&H(CH,) sec-Butyllithium CH3CH2CH(Li)CH3 Diisoamyl (CH&&HCH(CH,)a,a,a',a'-tetraaryl-4,5-dimethoxy1,3-dioxolane Iris-(Diethy1amino)sulfonium difluorotrimethyl silicate Tetrabutylammonium bromide n-Bu,N'BrTetrabutylammonium fluoride n-Bu,N'FTetrabutylammonium iodide n-Bu,N'It-Butyldimethylsilyl t-BuMe,Si f-Butylhydroperoxide Me3COOH
xi
xii t-Bu
TEBA TEMPO TFA TFAA Tf (OTf) THF THP TMEDA TMG TMS TMP TPAP To1 Tr TRIS Ts(Tos) x c
ABBRNIATIONS tert-Butyl Triethylbenzylammoniurn Tetramethylpiperdinyloxyfree radical Trifluoroacetic acid Trifluoroacetic anhydride Triflate Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine 1,1,3,3-Tetramethylguanidine Trimethylsilyl 2,2,6,6-Tetramethylpiperidine tetra-n-Propylammoniurn perruthenate Tolyl Trilyl Triisopropylphenylsulfonyl Tosyl = p-Toluenesulfonyl Chiral auxiliary
Me2NCH2CH2NMe2 -Si(CH3)3
VSP VOE
'was
EL LI
'Sd
I
N0113810Xd
I
861
6EP
ILP fIZ
OLP ilZ
OW 661
1Lt tlZ
LIP W1
LLE
LUC L91
is1
nLE CS1
6 s 891
EhE 691
WE LEI
LI)E 8fI
R9E 6CI
SEE CZ1
hEE PZI
OIE Lni
Pir 801
LIE 601
f6
SYZ
591 P6
9iz LL
OEZ 8L
6L
6EZ
E9 Oil 29
OZI
1Z1 C9
06 Lt
15 8P
86 6t
Ll
6
XI
ZE
01
81
01
61 61
Cf
hl Pf
,"
san!4r%uap P I P Jllh'xoqle3
I sl"ua~d'sl'WJIV
'apFqWv
I
I
I
I
562
550
695
6%
534
49Y
378
493
491
339 562
330
320
309
561
338
336 561
329 530
327 SIX
560
335
326
515
334 SM)
325 511
4')o
JYX
311 245
306 4x9
30s
316 497
315 4%
305 4x8
488
301
382 698
576
347
573
346
383 699
610
354 604
603
353
595
351
56%
344
592
350
343 565
342 565
702
384
630
625
340
359 624
(1x1
357
702
650,
365 644
642
364
Y
702
XIS
369 663
Y
/
703
387
669
372 667
I/ 704
388
689
/
/
389 705
70X
390
#' ,/
S e c t i o n s k a v y type Pages-light type
g I/
INDEX, DIFUNCTION AL COMPOUNDS
Blanks in the table correspond to sections for which no additional examples were found in the literature.
INTRODUCTION Relationship between Volume 11 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 7 7 presents 2781 examples of published reactions for the preparation of monofunctional compounds, updating the 13,050 in Volumes 1-10. Volume 11 contains 1212 examples of reactions that prepare difunctional compounds with various functional groups. Reviews have long been a feature of this series, and Volume 11 adds 41 pertinent reviews in the various sections. Chapters 1-14 continue as in Volumes 1-10, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6-10. The sections on oxides as part of difunctional compounds, introduced in Volume 7, continues in Chapter 16 of Volumes 8-1 1 with Sections 378 (Oxides-Alkynes)through Section 390 (Oxides-Oxides). Following Chapter 16 is a complete alphabetical listing of all authors (last name, initials). The authors for each citation appear below the reaction. The principal author is indicated by underlininq (i.e., Kwon, T.W.; Smith, MB), as done previously in Volumes 7-10. Classification and Organization of Reactions Forming Monofunctional Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in descending order of year cited (2001-1999), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains; for example, the reactions t-BuOH + t-BuCOOH, PhCH,OH + PhCOOH, and PhCH=CHCH20H + PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated ketones, aldehydes, esters, acids, and nitriles have been placed in Sections 74D and 74E (Alkyls from Alkenes), respectively. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H+ RCH,COOH (carboxylic acids from hydrides), RMe -+RCOOH (carboxylic acids from alkyls), RPh -+ RCOOH (carboxylic acids from aryls). Note the distinction between R2C0 + R2CH2(methylenes from ketones) and RCOR' RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (alkyls, methylenes, and aryls from alkenes). xv
xvi
INTRODUCTION
The following examples illustrate the classification of some potentially confusing cases: RCH=CHCOOH-+ RCH=CH2 -+ ArH + ArH -+ RCHO 4 RCH=CHCHO -+ RCHO -+ RzCH2 + RCH2COR -+ RCH=CH2 -+
RCH=CHz RCH=CHCOOH ArCOOH ArOAc RH RCH=CHp RCH3 R2CO RzCHCOR RCH&HS
RBr+HC=CH
RC=CR
-+
ROH + RCOOH -+ RCOOR RCH=CHCHO
-+
RCH=CHCN
-+
RCH2CH2CN
Hydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from methylenes Ketones from ketones Alkyls from alkenes (Hydrogenation of Alkenes) Acetylenes from halides; also acetylenes from acetylenes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Reduction)
How to Use the Book to Locate Examples of the Preparation of PJOtection of Monofunctional Compounds. Examples of the preparation of one functional group from another are found in the monofunctional index on p xiii, which lists the corresponding section and page. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of this index. Section 1 gives examples of the reactions of acetylenes that form new acetylenes; Section 16 gives reactions of acetylenes that form carboxylic acids; and Section 31 gives reactions of acetylenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1, 17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of acetylenes from acetylenes; carboxylic acids from carboxylic acids; and alcohols, thiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74E (Alkyls, Methylenes, and Aryls from Alkenes). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes from Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330
INTRODUCTION
xvii
(Alcohol, Thiol-Ketone). Examples of the synthetically important alkene metathesis reaction are mostly found in Section 209 (Alkenes from Alkenes). Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also presented. Sections (designated with an A: 15A, 30A, etc.) are labeled “protecting group: reactions” and are located at the end of pertinent chapters. Some pairs of functional groups such as alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In no instance should a citation in this book be taken as a complete experimental procedure. Failure to refer to the original literature prior to beginning laboratory work could be hazardous. The original papers usually yield a further set of references to previous work. Papers that appear after those publications can usually be found by consulting Chemical Abstracts and the Science Citation Index. Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrite, and alkene. Reactions that form difunctional compounds are classified into sections on the basis of two functional groups in the product that are pertinent to the reaction. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-amino-alcohols, 1,3-amino-alcohols, and 1,4-amino-alcohols are included in a single section (Section 326, AlcoholAmine). Difunctional compounds that have an oxide as the second group are found in the appropriate section (Sections 278-290). The nitroketone product of oxidation of a nitroalcohol is found in Section 386 (KetoneOxide). Conversion of an oxide (such as nitro or a sulfone moiety) to another functional group is generally found in the “Miscellaneous” section of the sections concerning monofunctional compounds. Conversion of a nitroalkane to an amine, for example, is found in Section 105 (Amines from Miscellaneous Compounds). The following examples illustrate applications of this classification system:
INTRODUCTION
xviii
Difunctional Product RC=C-C=CR RCH(0H)COOH RCH=CHOMe RCHF, RCH(Br)CH,F RCH(OAc)CH,OH RCH(OH)CO,Me RCH=CHCH,CO,Me RCH=CHOAc RCH(OMe)CH2S02CH2CH20H RSOZCHZCHZOH
Section Title Acetylene-Acetylene Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Aikene Ester-Alkene Alcohol-Ether Alcohol-Oxide
How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p xiv gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, Thiol-Ester) contains examples of the preparation of hydroxyesters; Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. Some preparations of alkene and acetylenic compounds from alkene and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, the transformation RCH=CHBr + RCH=CHCOOH could be considered as preparing carboxylic acids from halides (Section 25, monofunctional compounds) or preparing a carboxylic acid-alkene (Section 322, difunctional compounds). The choice usually depends on the focus of the particular paper where this reaction was found. In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Likewise, many citations for reactions found in the Aldehyde-X sections, will include examples that could be placed in the Ketone-X section. Again, the choice is dictated by the paper where the reaction was found. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. As an example, the reaction RCI + ROH might be used for the preparation of diols from an appropriate dichloro compound. Such methods are difficult to categorize and may be found in either the monofunctionalor difunctional sections, depending on the focus of the original paper. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. Compounds of the type RCH(OAc)CH,OAc (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH,OH (alcohol-alcohol).
INTRODUCTlON
xix
Sources of Literature Citations. I thought it would be useful for a reader
of this Compendium to see those journals that contain the most new synthetic methodology. The accompanying graph shows that Tetrahedron Letters, Organic Letters, and Journal of Organic Chemistry account for roughly 46% of all the citations in Volume 11. In past volumes, Tetrahedron Letters and Journal of Organic Chemistry have accounted for 50430% of all citations. The advent of the new journal Organic Letters, the consolidation of several European journals into the European Journal of Organic Chemistry, and the apparent expansion of synthetic methodology relative to the last two volumes probably accounts for the new relationship of the three cited journals. This book was not edited to favor one journal, section or type of
Citation Sources,Volume 11 950
900 850
800 7.50 700 650 600 550
g 500 .z u
a. .
.*
450 400
350
300 250 200 1 so 100 50 0
Journal
xx
INTRODUCTION
article over another. Undoubtedly, my own personal preferences are part of the selection, but I believe that this compilation is an accurate representation of new synthetic methods that appear in the literature for this period. Therefore, I believe the accompanying graph reflects those journals where new synthetic methodology is located. I should point out that the category “16 other journals” includes: Helvetica Chimica Acta, Journal of Heterocyclic Chemistry, Pure and Applied Chemistry, Journal of Chemical Research (S), Monatshefte fur Chemie, Russian Journal of Organic Chemistv, Acta Chemica Scandinavica, Israel Journal of Chemistry, Chemistry, A European Journal, Canadian Journal of Chemistry, Chemistry Letters, Chemical Reviews, Bulletin of the Chemical Society of Japan, Organic Preparations and Procedures International, Accounts of Chemical Research, Heterocycles, and the Australian Journal of Chemistry In addition, 6 more journals were examined but no references were recorded.
Cornpendium of 0rganic Synthetic Methods
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 1 PREPARATION OF ALKYNES
SECTION 1: ALKYNES FROM ALKYNES
+ 20% 1,4diphenyl-
19-hutadiyne Chow. 14.-F.; Wan, C.-W.; Low, K.-H.; Yeung, Y.-Y. J. Org. Chenz., 200Z, 66, 1910.
-
1. B uLi , KOt-Bu , THF hexane, -78°C -25°C
7
2. 2 eqMeI , .--43"C -+ rt
\
7
Kowalik. .I.Tolhert, ; L.M. J. Org. Chem., 2001, 66, 3229.
Ph
= 5% Pd,(dbah*CHCl3,
10% C U I ,rt 2 eq NaOMe , MeOWMeCN, rt , 3 h
S.-K;Kyu, 11.-C.; Lee. S.-14. Syntlz. Corrtrrzun., 200Z, 31, 1059.
74%
2
Section 1
Compendium of Organic Synthetic Methods, Vol 11
=
Ph
-
PhZI'BFL ,DME;JH,O , rt NaHC03, 30 min
hP-P
85%
S.-&; Yoon, S.-K.; Kim, Y.-M. Org. k t f . , 2001, 3, 2697.
&me.
=
Ph,Sb(OAc), , 10%CuI, 5 h
* 7 P 5% Pd2(dba),-CHCI3, MeCN 50°C Kanp.;Ryu, H.-C.;Hong, Y.-T. J . Chem. Soc., Perkin Trans. I , 2001, 736. ph
PhSe
SiMe3
=
CF3SiMe3, Bu4NF
CH(OEt),
+ Me3Si
=
Yoshimatsu.; Kuribayashi, M. J. Chem. SOC.,Perkin Trans. I , 2001, 1256. Me02C-
3. PhI, cat Pd(PPh3)4 -78°C -t 23"C, 3 h Org. Left.,2001, 3, 31 1 1 .
Anastasia, L.;
-
C6H13
*
MeOzC
88%
=
PhI, 2 eq TBAF, 2%CuI w
1% PdCl2(F'Ph3)2 ,THF, rt
-
Et3SiH , 1% Ir4(CO)12
GH13
* P h =
12% PPh3 . . Shimizu, R.; p u c h i k a u. Tetruhedron k t t . , 2000, 41, 907, PhBr , 3 %Pd(PhCN)2C12 6% P(t-BU), , 2% CUI
P h =
-Ph
= 93 %
=
SiEt3
Ph
1.2eq i-Pr2NH,It dbxane Fu. G . C . Org. Lett., 2000, 2 , 1729. Hundertmark, T.; Littke, A.F.; Buchwaid..L.: I
P h =
O
o
M
Ph
98 %
J'vlori. A.; Shimada, T.; Kondo, T.; Sekiguchi, A. Synlett, 2001, 649. Ph
81%
CH(OEt),
TIIF, 0°C
1. LDA ,THF 2. ZnBr, ,T I I F , -78°C
h
96%
94%
e , TIIF, 60°C
* P h - e O M e 0.5%Pdz(dba), , 2% PPh3 TBAF , 6 h Mon.;Kawashima. J.; Shimada, T.; Suguro, M.; Hirabayashi, K.; Nishihara, Y. Org. k t t . , 2000, 2, 2935.
\ /
83%
3
Alkynes from Alkynes
Section 1
Pd-CuI-PhP hdKF-A1203
94%
Kahalka.G.W,; Wang, L.; Namboodiri, V.; Pagni, R.M. Tetruhedron Lett., 2000, 41, 5151.
- -
BuLi, B(0i-Pr), , DME-THF + C6Hl, p-Tol-Br , 3 % Pd(PPh3)4
=
p-Tol
98% Kang, S.; Jang, T.-S.; Keum, G.; Kang, S.B.; Han, S.-Y.; K i m . O r g . Lett., 2000, 2, 3615. TMSCF3, cat CSF, THF
Ts- N
0.5 h quant
. . M.; IIoshino, 0. Tetruhedron, 2000, 56, 8657, 8661. w.
F h =
0.5% Pd2(dba), , NEt, , THF
-
F ' h - O A c
\ /
0.5% P(t-Buh , rt , 2 0 h
.p
Bohm, V.P.W.;
//
W.
>99%
. Eur. J. Org. Chem., 2000, 3619. Me0
\
2.5% Pd2(dba), , 20% CuI 20% 2,6-di-r-Bu-phenol DMF , i-PrzNEt , -20°C
MeOzC Nakamura, K.; Okuho, H.; Yamacuch i. M. Synlett, 1999, 549. K#&4-&03,
pentane +
\ =
flt,2h Cadclick. S.; Murtaugh, L.; Weacing, R. Tetruhedron Lett., 1999, 40, 3655
52%
Compendium of Organic Synthetic Methods, Vol 11
4
Section 4
0
6% (r-BuO),W C C t -Bu
bluene ,80"C
/
*
69%
Furstner.;Guth, 0.;Rumho, A.; Seidel, G. .IAm. .
Chem. SOC., 1999, 121, 11108.
SECTION 2: ALKYNES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 3: ALKYNES FROM ALCOHOLS AND THIOLS NO ADDITIONAL EXAMPLES
SECTION 4: ALKYNES FROM ALDEHYDES 1. CC13COOH, (TJl,COC-Na+
DMF ,35"C
*
2. TsCl , TENDABCO ,DCM ,25"C 3.4.5 eq MeLi , TI-IF , -10°C 9SX91X94% 4.&O+ Wanp.; Campagna, S.; Yang, K.; Xu, G.; Pierce, M.E.; Fortunak, J.M.; Confalone, P.N. J. Org. Chem., 2000, 65, 1889. 1. Ph3PCHBr2 Br , THF r-BuOK ,rt 2. r-BuOK
*
B
Michel. P.: Gennet. D.: Rassat, A. Tetruhedron Lett., 1999, 40, 8575.
G
C
C
H 66%
5
Alkynes from Halides
Section 10
1. LDA ,TIIF ; DCM , --78"C 2. TsCl , TEA, E M , 25°C
4. 3.3.5 II,O+ MeLi ,TIIF, -10°C *
Wane.; Yin, J.; Campagna, S.; Pesti, J.A.; Fortunak, SECTION 5:
e
x
9
3
x
9
1
%
J.M. J. Org. Chem., 1999, 64, 6918.
ALKYNES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 6:
ALKYNES FROM AMIDES NO ADDITIONAL EXAMPLES
ALKYNES FROM AMINES
SECTION 7:
NO ADDITIONAL EXAMPLES
ALKYNES FROM ESTERS
SECTION 8:
NO ADDITIONAL EXAMPLES
SECTION 9:
ALKYNES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES
SECTION 10:
+d
ALKYNES FROM HALIDES AND SULFONATES
OTf
t-Bu Ilalhes, IJ.; Bertus, P.;
Bu-aC-SiMe, ,TBAF cat Pd(PPh3)d , a t AgI 3 HZO, 21 h
t-Bu Tetruhedron LRtt., 2001, 42, 8641.
Section 10
Compendium of Organic Synthetic Methods, Vol 11
6
PhI, PdCuI-PPh3 ,neat
-SiMe3
P h = P h
*
KF-Al20, ,microwaves ,2.5 mm 90%
Kahalka. G.W,; Wang, L.; Pagni, R.M. Tetruhedron, 2001, 57, 8017.
,Pd(PPh3hCh
-SiMe3
G
L
\ I
EtzNH , DMF , microwaves 120°C , 5 min
I
S
i
M
A. J. Org. Chem., 2001, 66, 4165. 1. PhI, cat Pd(PPh,)4
Bu3Sn-
2. Merrifield resin , NaI
w
= 93%
Blomgren, P.A. Org. Lett., 2001, 3, 1869.
;-
=
Ph
SiMe,O€I
PhI, T H F , TBAF, 60°C
5% Pd(PPh3)4,2.5 h
* P h = 97%
Yang, S.H.; Lee, P.H. Tetruhedron Lett., 200Z, 42, 4833.
;&-
/
S ~ M0.5 Q AgC03 I o , 5 o% PM ~ ( OeA C ) ~i / P PP~ ~
Ph
PhI
O
Bu$rlCi ,THF, 65°C , 2 h
Koseki, Y.; Omino, K.; Anzai, S.; &ga&aL Li[-:B
B(Omh)3]
*
ph
Ph
M
e 92%
Tetruhedron Lett., 2000, 41, 2377.
5% Ptl(PPh3)4, 5% CUI 15h, DMF Oh. C&; Jung, S.H. Tetruhedron Lett., 2000, 41, 8513.
PB -r
REVIEW: “Formationof Acetylenes by Ring-Opening of 1,1,2-Trihalocyclopropanes,” Svdnes. L.K.Eur. J. Org. Chern., 2000, 3511.
94%
q
Section 14
7
Alkynes from Alkenes
SECTION 11:
ALKYNES FROM HYDRIDES
For examples of the reaction RC-CH (Alkyne- Alkyne).
4
RCEC-CECRI, see section 300
NO ADDITIONAL EXAMPLES
SECTION 12:
ALKYNES FROM KETONES 1. NaH ; TfzO 2. TFA
C ,()0B 2-tu
PhOI ,c 14
3. KzCO3, acetone, 4 h
reflux Ramarao, C. Chem. Commun., 1999, 1113.
SECTION 13:
-
WH,C),
72~68%
ALKYNES FROM NITRILES
x X=H 69% X=Me 73% Yoo. B.-WL;Lee, S.-J.; Choi, K.-H.; Keum, S.-R.; KO, J.-J.; Choi, K.4.; Kim, J.-H. Tetruhedron Lett., 2001, 42, 7287.
SECTION 14:
ALKYNES FROM ALKENES NO ADDITIONAL EXAMPLES
=
8
Compendium of Organic Synthetic Methods, Vol 11
SECTION 15:
Grasa, G.A.;
Ph
AIXYNES FROM MISCELLANEOUS COMPOUNDS
d'(oH)z ,Pdddba)3
=
-
Bu
Section 15A
SMe
Cu(I) -thiophene-2carhoxylate THF ,50°C
Bu
S.P. Org. Lett., 2001, 3, 119. 1 . BuLi, TIIF 2.PhCHO
S02Ph
*
-ph
3. Ac@ 4. LDA ,THF ,-78°C + rt 74% Orita, A,; Yoshioka, N.; Struwe, P.; Braier, A,; Beckmann, A,; O t e r a . C h e m . Eur. J., 1999, 5 , 1355.
SECTION 15A:
PROTECTION OF ALKYNES NO ADDITIONAL EXAMPLES
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 2 PREPARATION OF ACID DERIVATIVES
SECTION 16:
P h = Li, J.; Li, G.;
SECTION 17:
ACID DERIVATIVES FROM ALKYNES
c o , 3% 1 1 2 0 , cat PdCl2 2 eq CuC12, clioxane , rt , 9 h
*
ho 98%
0
0 Tetruhedron Lett., 2001, 42, 6923.
ACID DERIVATIVES FROM ACID DERIVATIVES HO ,C
I
in hexane + 12-c-4 Brun, E.M.; Gil, S . ; Yarra, M. Synlett., 2002, 156.
cqrr
(84
:
16) 85%
(30
:
70) 74d.
PPh3, C C I F N , DCM
NEt3,rt,1 h Kim.; Jang, D.O. Synth. Contrnun., 2001, 31, 395.
c1
89%
10
Compendium of Organic Synthetic Methods, Vol 11
C02H
Section 19
1 . 2 . 2 9 sec-BuLi, THF , -78°C 2. Me1 3. H2O
80% (90: 10) Mortier, J.; Vaultier, M.; Plunian, B.; Sinbandhit, S. Can. J. Chem. 1999, 77, 98.
SECTION 18:
c5H 11CH2OH
ACID DERIVATIVES FROM ALCOHOLS AND THIOLS Na2W04*2H 2 0 , Bu4NHS04
*
30% aq H z 0 2 ,microwaves, 20 mm Cukasiewicz, M. Synlett, 2000, 143.
C5HllC02H
75%
m;
PhCHZOH
1. TEMPO, MeCN ,35"C yodium phosphate buffer
PhCOzH 98% 2. NaCIO2 ,dilute bleach Zbao. M,;Li, J.; Mano, E.; Song, Z.; Tschaen, D.M.; Grahowski, E.J.J.; Reider, P.J. J. Org. Chem., 1999, 64, 2564. NaIO4 , R~Cl-pH20,EtOAc
* Ph-C02H MLCN/H~O Prashad. M.;Lu,Y.; Kim,H.-Y.; Hu, B.; Repic, 0.;Blacklock, T.J. Synth. Conzmun., 1999, 2Y, 2937. PhwoH
93%
SECTION 19: ACID DERIVATIVES FROM ALDEHYDES PhCHO
~ ~ i t H 2 ,0HCOOH 2
*
Pha2H
96%
rt,15h . . Balicki. B, Synth. Conimun.,2001, 31, 2195. PhCHO
N- hrnmophthali~nide-IIg(OAc),
Anjum, A,; & i u v a s.. P. Chem. Lett., 2001, 900.
; .H-
urea-H202 ,aq NaOH , 1 h P hCHO * Newhold, A.J. Tetrukdron Ldt., 2001, 42, 6607.
*
PhCOOII
PhCO,H
94%
94%
Section 20
11
Acids from Alkyls
H202-SeO2,
THF
reflux, 5 h
99%
Wcjjtowicz, H.; Brzpzcz, M.; Kloc, K.; Mlochowski, J. Tetruhedron, 2001, 57, 9743.
73% Sato, K.; Hytdo, M.; Takagi, J.; Aoki, M.; Noyor L& Tetruhedron k t t . , 2000, 41, 1439. bmnate exchange m i n
* PhCOOH octane, =flux Chetri, A.B.; Kalita, B.; Das. P.J, Synth. Commun.,2000, 30, 3317. PhCHO
€124
PhCXO
, cat S e 9 , T H F
*
PhCooH
*
PhC02H
reflux, 2.5 h Synth. Conmun., 2000, 30, 4425. PhCIIO
O2 , A1203,micluwaves
Reddy, P.P.; &ddv. P.S.N. Synth. Commun.,1999, 29, 2949. Reddy, D.S.;
SECTION 20:
97%
58%
ACID DERIVATIVES FROM ALKYLS, METHYLENES AND ARYLS C O , V q a c a L h ,K2S208 CF3CO0I-I
CH't
88%
+
CH,COOH
93%
Taniguchi, Y.; Hayashida, T.; Shihasaki, H.; Piao, D.; Kitamura, T.; Yamaji, T.; Org. Lxtt., 1999, 1, 557. Ph-- CH3 ,
'
0.5 clo, ,35eq €I@,
Ph-H
MtCN,rt, 1 h Org. LEtt., 1999, 1, 2129. NaOCI,MeCN,rt,I h
02N-@.
. .
* Synth. Commun., 1999, 29 , 2211.
85%
CO,H 98%
12
Section 23
Compendium of Organic Synthetic Methods, Vol 11
SECTION 21: ACID DERIVATIVES FROM AMIDES PhCON HNMe,
2 qPhI(OH)OTs,
H20
t
91%
wuts. P . m ; Gohle, M.P. Org. Lett., 2000, 2, 2139.
+&
ji
Ph
250°C, 4 atm
/
NH2
*
30 min
Ph O H' 99%
0
+ phthalimide
TerrohedronLeft.,2000, 41, 3855.
SECTION 22: ACID DERIVATIVES FROM AMINES NO ADDITIONAL EXAMPLES
SECTION 23: ACID DERIVATIVES FROM ESTERS
($
co2i-pr
AlC!, , MeNO,
H 2oc$(
10"C,ld
92%
N HC02i- Fr Chee, G.-L. Synlett, 200Z, 1593. C e l C02t-Bu
N€IC02i- Pr
SiO, , toluene ~ f l u x7, h
* C
Buck, M.;
1. BuLi , THF
\0 C/ O
2
H
74%
R.W, Tetruhedron k t t . , 2001, 42, 5163. =-UB
I
t
B-CloH21
2. CloHzlI, reflux, 8 h Tetmhedron k t t . , 2001, 42, 5825.
75%
Section 25
13
Acids from Halides
-
1. ZnBr,, DCM , 1d
P hCnzt-Bu
PhCO,H 2. HzO , 2 h Wu.Y-0,; Limhurg, D.C.; Wilkinson, D.E.; Vaal, M.J.; Hamilton, G.S. Tetruhedron Lett., 2000, 41, 2847.
86%
irzo
so,,
* PhCHzCQH microwaves Ranu.; Dutta, P.; Sarkar, A. Synth. Conzmun., 2000, 30, 4167. PhCHZC02Me
PhSH ,KZCD3,NMP
PhC0,Me
+
PhCO,II
190"C, 10 min Tetruhedron, 1999,55, 9595.
Shar~na,L.; Nayak, M.K.;
92%
quant
Other reactions useful for the hydrolysis of esters may be found in Section 30A (Protection of Carboxylic Acids).
SECTION 24:
ACID DERIVATIVES FROM ETHERS, EPOXIDES AND THIOETHERS
A0
P 11
Bi(II)mandelate ,0, , DMSO +
R'yc%Er , 80°C ,4.5 h OH
Coin, C.; Le Boisselier, V.;Favier, I.; Posbel, M.;
SECTION 25:
PhCHZCl
PhC02kI
c h/3 h Hiram T.; Morimoto, C.; Takada, T.; Sakurai, H. Tetruhedron Lett., 2001, 42, 1961.
PhCH=N-OI 1
*
PhC02H
99% 30% HzOz, THF , reflux, 10 h Synth. Contmun., 2001, 31, 3151. Giurg, M.; Said, S.B.; Syper, L.; m c h o w &iJ
REVIEWS: "Carboxylic Acids and Esters,"
J. Chem. Soc., Perkin Trans. 1, 1999, 3537
eJ
Section 30A
SECTION 30A:
Protection of Acids
17
PROTECTION OF CARBOXYLIC ACID DERIVATIVES
NaH,DMF,rt
~
92% o-Wu. M&; Regueiro-Ken, A.; St. Laurent, D.K.; Carroll, T.M.; Balasuhramanian, B.N. Tetruhedron Lett., 200Z, 42, 8593.
THF, rt Wang, M.F.; Golding, B.T.; Potter. &A. Synth. Commun., 2000, 30, 4197. Other reactions useful for the protection of carboxylic acids are included in Section 107 (Esters from Carboxylic Acids and Acid Halides) and Section 23 (Carboxylic Acids from Esters).
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 3 PREPARATION OF ALCOHOLS
SECTION 31: ALCOHOLS AND THIOLS FROM ALKYNES NO ADDITIONAL EXAMPLES
SECTION 32:
ALCOHOLS AND THIOLS FROM ACID DERIVATIVES OH MeCHO
Y
O0 z
H phenylpyruvate decarboxylase 0 76% (87% ee) Tetmhedron Asymm., 2001, 12, 571.
Guo, Z.; Goswami, A.; Nandur, V.B.;
BnEt,N+BF; , reflux, DCM
B uCO~ZI
Ndrdslmhdn.; , , . . Swarnalnkshmi, S.; Balakumar, R. Synth.
-
PhS02C1
>
70%
Commun., 2000, 30, 941.
3.5 q Zn + Me$iCI2, 3 eq DMA 1.2DCE,75"Ct 15 h
DMA = dimethylacetamide IJchiro, 11.; Kohavashi. S, TetruhetEronZxtt., 1999, 40,3179.
Ph
CO,H
BuCH~OH
-
PhSH
95 %
c1 1.
a
&(" N A N
,DME*fl
N-methylmorpholine , 3 h 2. NaBH4, H20 , 0°C
*
-OH Ph
Falorni.;Porcheddu, A.; Taddei, M. Tetmhedron Lett., 1999, 40,4395.
92%
Section 34A
19
Alcohols from Aldehydes
SECTION 33:
ALCOHOLS AND THIOLS FROM ALCOHOL AND THIOLS
1. haeSO$l,
i
DCM ,25"t
2. LiA1H4, THF
&
OH
C,H ,,CH,CH,OH
47%
OH
Benedetti. F.; Norhedo, S. Tetruhedron Lett., 2000, 41, 10071.
" F A A , MeCN h ydroslfide -supported polymer re sin
+
C$,,CH2CH2SH 85%
Sadavarte, V.S.; Uppalla, L.S. Chem. Lett., 2000, 1304.
;-
SECTION 34: ALCOHOLS AND THIOLS FROM ALDEHYDES The following reaction types are included in this section: A. Reductions of Aldehydes to Alcohols B. Alkylation of Aldehydes, forming Alcohols. Coupling of Aldehydes to form Diols is found in Section 323 (Alcohol-Alcohol). 1. CF3SQH-THF t PhCH,OH 83% 2. Z-BUNHZ-BH~ Lukln.;Yang, C.X.; Bellettini, J.R.; Narayanan, B.A.; Leanna, M.R.; Rasmussen, M. Synlett, 1999, 59.
PhCH2(OMe)2
SECTION 34A: PhCHO
REDUCTIONS OF ALDEHYDES TO ALCOHOLS Ph3PBu+BH4-, DCM ,rt
b
PhCH,OII
&ygmur. A .R.;Mallakpour, S.E. Synth. Commun., 2001, 31, 1177. PhCHO
Yu,H.;
PhB(0II)L ,Bu3Sn€I,DCM rt , 4 h
Synth. Cornmun. 2001, 31, 2719.
t
94%
PhCHzOH 88% (15% without PhB(OH)2)
20
Section 34A
Compendium of Organic Synthetic Methods, Vol 11
3 eq HC02Na, H@
CHO
58%
34OoC-35O0C B r y a n . T.A.; Jennings, J.M.; Gibson, J.M. Tetruhedron Lett., 2000, 41, 3523. Mg-FeCb , aq DMF
P hCI I 0
LPhCHzOH rt,25h Swami. s.s.; Desai, D.G.; Bhosale, D.G. Synth. Commun., 2000, 30,3097.
[emim] PF, ,B B u 3 , 16 h
PhCHO
92%
PhCH,OH
L-
quant
ionic liquid medium
Kabalka.;Malladi, R.R. Chem. Commun., 2000, 2191. PhCHO Liu, W.-y.; Xu, Q.-h.;
NaBH4, SiOz ,rt , 10 min
LPhCH20H Org. Prep. Proceed. Int., 2000, 32, 596.
Bu3SnH ,MeOH
-CHO Ph ~.
L-
P
h
96%
M
O
reflux quant
Kamiura, K.; Wada. M. Tetruhedron Lett., 1999, 40, 9059. PhCHO Bagnell, L.;
i-PiOH ,225"C, 1 d
*
PhCHzOH
92%
t
PhCH,OII
90%
Chem. Commun., 1999, 281.
IKHO , NaOH, 25 sec
PhCHO
microwaves Thakuria, J.A.; Baruah, M.; Sandhu. J.S. Chem. Lett., I999, 995. Zn , BnNE4C1, MeOH
-
PhmzOH reflux,4 h Kardile, G.B.; Desai, D.G.; Swami. S.S. Synth. Commun., I999, 29, 2129. PhCHO
P hCI I 0
1 . SnC12-2 IIzO, Mg , THF 2. H Z 0
Bordoloi.;Sharnia, R.P.;
PhCHzOH
Chakraborty, V. Synth. Commun., 1999, 2Y, 2501.
90%
90%
H
Section 34B
21
Alcohols from Aldehydes
ALKYLATION OF ALDEHYDES, FORMING ALCOHOLS
SECTION 34R:
ASYMMETRIC ALKYLATIONS Ti(Oi-Pr), , TIIF , AlEt3 PhCHO
* tE' chiral sulfonated amino Ph alcohol ligand , 0°C You, 1 . 4 . ; Hsieh, S.-11.; Fau. €I.-M. Chem. Comrnun., 2001, 1546. 1.
/ASiMe, , cat TiF, , 0°C
kHO
OTIF'S
S-BINOL, DCM
2. aq HF ,MeCN
Bode, J.W.; Gauthier Jr., D.R.;
PhCIIO
-
4
*
Lt
EtzZn, his-amino-alcohol , 0°C toluene
=-
Ph
0.65 PhzZn , Et,Zn, 10°C toluene, chiral Re catalyst
97% (98% ee) J.P.; Raabe, G.
Angew. Chem. Int. Ed., 2001, 40, 1488.
E@,
Kj' 93% (84% ee)
Bolm.;Kesselgruher, M.; Hermanns, N.; Hildehrand,
P hCI I 0
OTIPS 011
Chem. Commun., 2001, 2560.
Ooi, T.; Saito, A,; Maru oka. K . Chem. Lett., 2001, 1108.
a-
98% (96% ee)
toluene-hexane ,rt
5% 2-azanorbornyl+xazolidine catalyst
Nakano.;Okuyama, Y.; Iwasa, K.; -Heterocycles, &SnBu3
PhCHO chirai phosphine-AgOTf , TI-IF
84% (88% ee)
u
'ph
L =L Ph
72% (77% ee)
2001, 54, 411.
Ph
88% (96% ee)
Yanagisawa, A.; Nakashima, €1.; Nakatsuka, Y.; Ishiba, A.; Bull. Chcvn. Soc. Jpn., 2001, 74, 1129.
22
Compendium of Organic Synthetic Methods, Vol 11
QH -
-
EtzZn ,hexane, toluene ,rt
P hCHO
15%chiral amino-alcohol , 1 d*
2 eq EtzZn , PhMehexane ,0°C 2% his(oxazo1me) ligand , 4 5 h
Schinnerl, M.; Seitz, M.; Kaiser, A.;
97% (72% ee)
ph&
Liu, D.-X.; Zhang, L.-C.; Wang, Q.; Da, C.-S.; Xin, Z.-Q.; A.S.C. Org. Lett., 200Z. 3, 2733.
PhCHO
Section 34B
Wane.;Choi, M.C.K.;
*
Chan,
96% (93% ee)
Ph Et Org. L.ett., 2001, 3, 4259.
Sp--L48% (>99%ee,S)
PhCIIO
10%TSA*HzO12O"C, 20 h Ph Ohga, M.; Nakamoto, H.; Matushara, T.; Hussain, I.; Kataoka, K. J. Am. Chem. SOC., 2001, 123, 9168. CIIO
NO, 68% (76%ee) Sakthivel, K.; Notz, W.; Bui, T.; Barhas III, C.F. J. Am. Chem. SOC.,200Z, 123, 5260.
P hCI I 0
ZnEtz, norephedrine thiol ligand
98% (99% e e , R)
toluene * PhEt' Jimeno, C.; Moyano, A.; PericBs. M.A.; Riera, A. Synlett, 2001, 1155. m S n B u 3
PhCHO Kii, S.; &uuhJ.
-L
, CHzClz, 0°C
95% (99% ee ,S)
Ti(IV) catalyst, 2h Ph Tetruhedron k t t . , 2001, 42, 1935. 2 eq E t2Zn
PhCHO
chiral amino-alcohol Hermsen, P.J.; Cremers, J.G.O.; Thijs, L.;
*
JEt 99% ( 9 2 % e e , S ) Ph TetruhedronLett. 2001, 42, 4243.
Section 34B
23
Alcohols from Aldehydes
, SiC14,6 h
-SnBu3
QH -
-
.-
P hCHO 5% chiralphosphoramide , -78°C
85% (79% ee)
-L -L
Denmark.;Wynn, T. J. Am. Chem. Soc., 2001, 123, 6199. EtJn, toluene, 0°C
PhCtIO
cat bis-f5-amino-alcohol
Xu, Q.; Wang, H.;
92% (95% ee S)
v.; Chan, A.S.C.; Yang, T.-k. Tetruhedron Lett., 2001, 42, 6171.
-
T i - c h i r al diol , hexane
P hCHO
Ph
97% (91% ee) Et,Zn , 0°C rt Ph Yang, X.-w.; Shen, 1.-h.; Da, C.-s.; Wang, H.-s.; Su, W.; Liu, D.-x.; M(ane.; Choi, M.C.K.; Chan, A.S.C. Tetruhedron Lett., 2001, 42, 6573.
PhCIIO
Et&,
c h i d amino-alcohol
-
QH
*
hexane ,0°C PhAEt ' Tetruhedron, 2001, 57, 4825.
Ohga, T.; Umeda, S.;
97%ee,R
Et,Zn, 10%(C,F,,CI12CH,),C-OII
90% (83% ee ,R )
P hCI I 0 toluene-hexane , rt ,20 h
. ,
; -
* PhtE'
Okumura, K.; Ohgo, Y. Tetruhedron, 2001, 57, 5565. Et,Zn ,toluene , 0°C
\ /
15% c h i d pyrrolidinylmethanol derivative
Zhao.; I,i,
X.-G.; Wang, X.-R. Tetruhedron Asymm., 2001, 12, 399.
P hCI I 0
B
~
~
O
,Zn A , qC NII,Cl
22°C
Lomhardo.;Girotti, R.;
Morganti, S.; m
i n
*
96% (93% e e , SS)
Jp
Ph
OAc 90% (65:35 syn:anti) .i .. C. Chem. Commun., 2001, 2310.
Compendium of Organic Synthetic Methods, Vol 11
24
PhCHO
EL,&, 5% sulfinyl ferrocene ligand toluene, rt
Section 34B
Ipri\/
c
80%(88%ee)
Ph Chem. Commun., 2001, 2026. ~~
Priego, J.; Manchefio, O.G.; Cahrera, S.;
PhCHO
Et,Zn, toluene, hexane
96% (83% e e , R) 20% chiral quinoline 0°C- It Xu, Q.; Wang, G.; Pdn.; Chan, A.S.C. Tetmhedron Asymm., 2001, 12, 381. &Br
YH
, S b , 0.5M HCl , H20
eL
Li, L.-H.; Chan, T.H. Cun. J. Chem., 2001, 79, 1536.
PhCHO
Et,Zn , toluene, 0°C , 7 8 h
cat iron tricarhonyl-amino alcohols
ph
67% (89% e e , 5') Okanioto, K.; Kimachi, T.; Ihuka, T.; Takemoto. Y . Tetruhedron Asymm., 2001, 12, 463.
I'hCHO
Et,Zn ,Ti(0i-Pr), , bluene chiral amine, MS 4 A , -30°C
i"
*
phA Et
1. CICH2CICH, MII, TMSCl
P hCI I 0
10% Cdsalen) , MeCN
-
2. fl+ , THF Bandini, M.; ; Mechiorre, P.; Tino, R.; Tetmhedron Asymm., 2001, 12, 1063.
P hCI I 0
2 eq ZnEt2 , toluene, rt
quant (59% ee)
2 ,
Lake, F.; &lohere. C , Tetruhedron Asymm., 2001, 12, 755.
58% (56% ee)
Ph
ptl,
99% (87% ee , S) cat binaphthylazepine lipillid Ph Superchi, S.; Mecca, T.; Giorgio, E.; Tetruhedron Asymm., 2001, 12, 1235.
PhCHO
2.2 eq EtJn, toluene, -30°C chiral amino-alcohol ligand
-1
Et Ph Cohb, A.J.A.; Marson. C.M. Tetmhedron Asymm., 2001, 12, 1547.
99% (64% ee)
PhCHO
25
Alcohols from Aldehydes
Section 34B
/IEt
2.2 eq EtzZn , toluene , 0°C , 7 h
* Ph
dendritic BINOL-Ti catalyst
99% (84% ee)
Fan.; Liu, G.-H.; Chen, X.-M.; Deng, G.-J.; Chan, A.S.C. Tetruhedron Asynim., 2001, 12, 1559.
PhCHO
Et,Zn , toluene, 43 h
* J 10% chiral ferrocenylph amino-alcohol ligand Bastin, S.; Aghossou-Niedercom, F.; Brucard, J.; E%&LL, Tctrulicdron A.syni.nz.2001, 12, 2395.
quant (83% ee)
t
JEt
1. Et,Zn, P-cillholine esterligand
PhCHO
E
toluene, rt
2. H30+ Ph a u . H.J.; Zhao, B.T.; Zuo, G.-Y.; Pittman Jr., C.U.; Dai. W.M.: Hao. X.J, Tctruhedron Asymin. 2001, 12, 2613. Et,Zn, Ti(Oi-Pr), , DCM , rt , 1 h
74% (39% ee)
quant (96% ee , R)
oCHo PhCHO
chiral sulfonated amino-alcohol * PhE t' You, J.-S.; Shao, M.-Y.; Gau. 1L-K Tetruhedron Asymm., 2001, 12, 2971.
BH
E M , 20"C, 19 h
/
PhNMe, , chiral Al compkx
63% (43% ee) Gothelf, A.S.; Hansen, T.; J!Argensen, K.A. J. Chem. SOC., Perkin Trans. 1, 2001, 854.
P hCHO Sato, I.; Saito, T.;
PhCAO
Et+,
neat
chiral amino-alcohol
-1 Ph
Et
99% (87% ee)
Chem. Commun., 2000, 2471. 2 eq Et2Zn , toluene ,rt , 1 d
5% chirdl amine hicyclo[2.2.l]heptme alcohol *
tE' Ph
99% (94%ee) Hanya, N.; Mino, T.; Sakamoto, M.;Euj&iJl Tetruhedron Lett., 2000, 41, 4587.
26
Compendium of Organic Synthetic Methods, Vol 11
Et,Zn ,5% chiral piperidine hexane, 0°C
PhCHO
Section 34B
88% (24% ee, S)
*EthP'
Shl.;Jiang, J.-K.; Feng, Y.-S. Tetrahedron Asymm., 2000, 11, 4923. g\/SnBu3
PhCHO
, aq EtOH , 4 O " C
*
(9-tolyl-BINAP , AgN03, 14 h 93% (79% ee)
Loh. T.-P.; Zhou, J.-R. Tetruhedron Lett., 2000, 41, 5261. 20% bis-naphthyl , hexane Et
Ti(Oi-Pr), ,45"C perfluom(m thyldecalm) Tian, Y.;
Ph
99% (54% ee)
Tetrahedron L.ett., 2000, 41, 8813.
=
CHO
1. allyldialkoxytitanium complex ether, -78°C
2. HzO
Bouzhouz.;Pradaux, F.; cossV.;Ferroud, C.; Falguibres, A.
53% (96% ee)
Tetruhedron Lett., 2000, 41, 8877. 1) PhMezSi
QIi -
---
BOW),
MeCHO 2) I I 2 0 2 , pH 6 huffer 3) Na$03, 0"
*
80% (93%ee)
SiMqPh h u s h . W.R; Pinchuk, A.N.; Micalizio, G.C. Tetruhedron Lett., 2000, 41, 9413.
P hCIiO
Et,Zn ,toluene, rt , 12 h
*L
chiral carbohydrate derivative Ph U.B.T.; Chun, Y.S.; Yang, W.K. Tetruhedron Asymm., 2000, 11, 2149.
83% (90% ee)
l.ZnPh@nEt, 5%chiral femcenyl catalyst 2. workup
92% (95% ee) Bolm. C.; Hermanns, N.; Hildebrand, J.P.; Muiiiz, K. Angew. Chern. Int. Ed., 2000, 39, 3465.
Section 34B
27
Alcohols from Aldehydes
AlEti ,THF, 12 h
PhIIO
OH
I
r
Ti(IV)-TADDOL ate complex Ph Lu, J.-F.; YOU,J.-S.; - Tetruhedron Asymm., 2000, 11, 2531. i-Pr,Zn , a morpholino-xylofuranose
C&,,CHO
-1
88% (96%ee)
toluene, 0°C , 8 h
i-Pr
C6H13
Yang, W.K.; W L B.T. Tetruhedron Asynzm., 2000, 11, 2947. 2 eq Et2Zn , 5 %chirdl amino-alcohol
PhCHO
* tE'
toluene , rt Hanyu, N.;Aoki, T.; Mino, T.; Sakarnoto, M.; Tetruhedron Asymm., 2000, 11, 2911.
PhCHO
. .
99% (93%ee)
Ph
Et2Zn , 6 %hydioxy-henzylamine
93% (89%ee)
toluene, rt Tetruhedron Asymm., 2000, 11, 3361.
Ph
/IEt
Et2Zn, cat chiral amino-alcohol
PhCHO
94%(84%ee)
*
92% (77%ee) Ph Wu. Y.; Yun, H.; Wu, Y.; Ding, K.; Zhou, Y. Tetruhedron Asymm., 2000, 11, 3543.
PhCI 1 0 ;-
toluenehexane , 5 h
polymer-hound BINOL, catalyst Et,Zn, Ti(0i-Pr), ,DCM ,0°C
* QEI
---
*
Ph Shin, Y.-J. Tetruhedron Left., 2000, 41, 9515.
92% (95%ee)
Et,Zn , toluenelhexane , 5 h C
I
O
C
H
O cat amino-alcohol
97% (91.5% ee) Yun, H..; JVu. Y.;Wu, Y.; Ding, K.; Zhou, Y. Tetruhedron Lett., 2000, 41, 10263. PhCHO
2 eq EtzZn, cat chiral amino-alcohol toluene , 2 h
Hanyu, N.;Aoki, T.; Mino, T.; Sakamoto, M.; Tetruhedron Asynim., 2000, 11, 4121.
99% (93%ee) tE' Ph
Compendium of Organic Synthetic Methods, Vol 11
28
Section 34B
,Ti(0i-F'r)d
/ m S n B u 3
Jhthyl , toluene
25°C , 2 0 h
Doucet.
L;Santelli, M. Tetruhedron Asymm., 2000, 11, 4163. Et,Zn, rt , 1 d
PhCIlO
- *
cat hrdged chiral amino-alcohol Arroyo, N.; Haslinger, U.; Mereiter, K.;
'
tE' 84% (96% ee) Ph TetruhedronAsymm., 2000, 11, 4207.
1 . Et,Zn , cat thiazolidine derivative PhCHO
2. H+
?I I
J ,
99%(89%ee)
Ph Et Meng, Q.; Li, Y.; He, Y.; Gum. Y,Tetruhedron Asymm., 2000, 11, 4255. PhCIIO Shen, X.; Guo, H.;
PhCHO
EtzZn, BINOLcatalyst , DCM
* tE' Ti(Oi-h)4, -7O"C, hexane Ph Terruhedron Asymm., 2000, 11, 4321. Et,Zn , c h i d amino-alcohol
* Ph .I. Org. Chem., 2000, 65, 2108.
toluene , 1 8 T , 20 min
Palco, M.R.; Caheza, I.;
*
96% (91% ee)
98% (97% ee , S)
3 eq E tzZn ,TIIF , -20°C AcO
-L
1 . .A ; Adiuns, N.D. J. Org. Chem., 1999, 64, 5201. PhCIlO
Br
,Ce(OTf)4-xHz0
75% (95 : 5 anti:syn) 90% ee
chiral ligand Ph L h . T.-P-; Zhou, J.-R. Tetruheclron Lett., Z999, 40, 9115.
90% (92% ee ,R)
Section 34B
Alcohols from Aldehydes
29
* L E*!%
Et2Zn, toluene , 0°C , 3 h PhCHO
Ph
HO-
quant (97% ee ,S)
Reddy, K.S.; Sol& L.; Moyano, A.;
; Riera, A. J. Org. Chern., 1999, 64, 3969.
,M&H, -20°C
&si(oMeh
; 80% (94% ee) catR-Tolyl-BINAP-AgF , 4 h ph Yanagisawa, A.; Kageyama, H.; Nakatsuka, Y.; Asakawa, K.; Matsumoto, Y.; Angew. Chem., Int. Ed., 1999, 38, 3701.
PhCIiO
p
EtzZn , 2 % chiral amino-alcohol PhCHO
t
0°C ,toluene, 5 h Ph €ho. F3.T.; Chun, Y.S. Synth. Cnmmun., 1999, 29, 521.
M
e
\ 0/
0 CHO
PhzZn, toluene, -3O"C, 1 d cat (chiral diary1 carbonate
+ ZnEt2) 84% (93% ee)
Huang W.-S.; &-L. J. Org. Chern., 1999, 64, 4222. 2 eq Et2Zn , toluene/DCM, rt PhCHO
polymer bound aziridinylmethanol
ten Holte, P.; Wijgergans, J.-P.; Thijs, L.; Br ,T€IF/hexane
P hCHO
88% (83% ee ,R)
In , h c h o n i i e
L,
91%(96%ee,S) Ph
-L Ph
Org. Lett., 1999, I, 1095.
73% (72% ee ,S)
x~~
Loh. T.-P.; Zhou, J.-R.; Yin, Z. Org. L t t . , 1999, 1, 1855. 2 eq Et2-Zn
PhCHO 5%
+&lH
N I Trt Gadhwal, S.; Baruah, M.;
Ph *
L, Ph
Synlett, 1999, 1573.
90%(99%ee)
30
Compendium of Organic Synthetic Methods, Vol 11
P hCI I 0
&SnBu3
bL
, DCM ,rt
5% (S, S-(PhebOX)F&Clz(HzO) Motoyama, Y.; Narusawa, H.; Nishiv
Section 34B
Ph
88% (61% ee) Chem. Comnzun., 1999, 131.
(84 >950/0ee
16 dr) 55%
'
Barrett. A.G.M,; Braddock, D.C.; de Koning, P.D. Chem. Conmsun., 1999, 459.
Iltl,
Et,Zn , hexane ,0°C -t rt
PhCHO
10% chirdl pyrmlidine
* Ph 97% (97% ee) Yang, X.; Shen, J.; Da, C.; Wanp.; Choi, M.C.K.; Yang, L.; Wong, K.-y. Tetruhedron Asynzm., 1999, 10, 133. chiral amino alcohoL-2 BuLi
PhCHO Schon, M.;
THF , -78°C , 1h &gf&
PhCfIO
*I Ph
Tetruhedron Asymm., 1999, 10, 169.
Bu
17% (71% ee)
BuLi ,c h i d bis-amide, -1 16°C
* PhBu' 72% ee Arvidsson, P.I.; Davidsson, 0 ;nilmenson. G. Tetruhedron Asymm., 1999, 10, 527. DEE/DMM
C N - B n
P hCI I 0
Et,Zn , hexane , 0°C
5% c h i d azetidine
*
99% (92% ee)
tE' Ph
Shi.;Jiang, J.-K. Tetruhedron Asymm., 1999, ZO, 1673. PhCI-IO
Et,Zn ,0°C , 3 0 h
81% (>99% ee)
chiral disulfide ligand * PhtE' Braes.; Appelt, H.R.; Schneider, P.H.; Sliveira, C.C.; Wessjohann, L.A. Tetruhedron Asymm., 1999, 10, 1737.
Section 34B
Alcohols from Aldehydes
31
2 eq E tzZn , 2 d , toluene ,0°C
PhCHO
Ph tE' 5% chird pyridyl alcohol Kanrr.; Kim, H.Y.; Kim, J.H. Tetruhedron Asymm., 1999, 10, 2523.
JEt
Et,Zn , toluene, 0°C P hCHO
82% (90% ee)
86% (95% ee)
*
chiral2,2'-bipyridyl diol Ph Kwonr. H .-J,.; Lee, W.-S. Tetruhedrnn Asynim., 1999, 10, 3791.
PhCHO
Et,Zn , toluene , -30°C
92% (78% ee)
10% camphor-derived
EPhxEt 1,4-amino-alc~hol K d b u k J L ; Ferencic, M.; Giirtner, P. Tetruhedron Asynim., 1999, 10, 3969.
LEt
2.2 eq EtzZn, toluene ,0°C
PhCEIO
91% (88% ee) cat Cinchona alkaloid *Ph Lee, S.H.; Im, D.S.; Cheon B. C.S.; Chung, B.Y.Heterocycles, 1999, 51, 1913. CHO
lOeq-SiC13
,HMPA
chiral DCM, amide-78°C , HMPA , 7 d * +(76%ee) Iseki. K.; Mizuno, S.; Kuroki, Y.; Kohayashi, Y. Tetrulzeclron, 1999, 55, 977.
PhCHO
Et,Zn ,toluene, 0°C ,70h
2% polymer-supported ephedrine Ph 85% (83% ee) derivative Sung, D.W.L.; Hodge.;Stratford, P.W. J. Chem. Soc., Perkin Truns. 1, 1999, 1463
NON-ASYMMETRIC ALKYLATIONS 1. 3 eq BuL-LiDMAE hexane ,-60°C. 1 h
*
~
2. t-BuCHO, THF -GO"C, 1 h Choppin, S.; Gros, P.; Fort. Y. Eur. J. Org. Chem., 2001, 603.
z
-
B
u 69%
OH
Compendium of Organic Synthetic Methods, Vol 11
32
PhCIIO
& Ph,
-SIB%
Section 34B
P
+
h
y
cat Bu4NBr-Ph12, H 2 0
OH
2-allyltin gives 9 3 7 syntunti
OH
(90 10) 80% Shihata, I.; Yoshimura, N.; Yabu, M.; Baha. & Eur. J. Org. Chem., 2001, 3207.
CTH15CHO
1. I
w
B
r ,In
+
2. Phl, cat Pd(PPh3)4,LiCl Hirashita, T.; Yarnamura, H.; Kawai, M.;
CH ' 15?Fb
43%
OH
Chent. Conttitun., 2001, 387.
PhCHO , aq THF ,70"C , 7 2 h 3 eq SnCJ , cat Pd(PhCN),C12
Uph 0
Ph\s//
*
65%
Tetruhedron Asymm. 2001, 12, 1625.
Mh-quez, F.; Lleharia, A.;
3. P-TsOH ,PhH ,80"C
22%
Soai.;Konishi, T.; Shihata, T. Heterocycles, 1999, 51, 1421.
m
B
r
,p-sno
CRO a t PtCl2(PPh3k , 4TIIF Sinha, P.;
PhCHO Pourhaix, C.; .
Chenz. Cornmun., 2001, 1798.
c1
1
H>-i , DME F , H2O Td ~
3% R ~ ( x x ) ( C O ) ~ ,3% dppf ,80"C Ph F.: ' Org. Lett., 2001, 3, 803.
p-To1
62%
PhCHO
33
Alcohols from Aldehydes
Section 34B
YHJC
awe,
1. IO%Cr-salen , 10%,Mn,TMSCl d e n , MeCN
Ph
2. H* ,TIIF
C1
40%
ph
Bandini, M.; $lg&UL ; Melchiorre, P.; Morganti, S.; Umani-Ronchi.. Org. Irtt., 2001, 3, 1153.
5%
PhBr ,NiBr,*hipy PhCHO
t
ph
65%
Maz
Ph DMF ,e-,FdCr/Ni anode Durandetti. M.;N6dClec, J.-Y.; PBrichon, J. Org. Lett., 2001, 3, 2073.
-
Et,Zn, cat Ni(acac)z, rt
Zn ,hexane/TEIF, 15 min
Shihata, K.; Kimura, M.; Shimuzu, M.; Tarnaru. Y. Org. Lztt., 2001, 3, 2181.
Top;\\
SnCl, ,-78°C
CHO
-
IIH $
PMP 0
60%
N\
PMP
Alcaide.;Pardo, C.; Rodriguez-Ranera, C.; Rodriguez-Vicente, A. Org. k t t . , 2001, 3, 4205.
mso, B(C,FS), - 7 8 c CHzClz ,ether 9
81% vinylogous Mukaiyama aldol Tetruhedron Lett., 2001, 42, 1269. Chirstmann, M.;
Section 34B
Compendium of Organic Synthetic Methods, Vol 11
34
OH PhCHO, C C l ,
Ph-m3
lt,THF
Barma, D.K.; Baati, R.; Valleix, A.; .-
A
C... F,
91% U Org. Lett., 2001, 3, 4237.
1. Li ,DTBB , t-BuCHO THF ,-78°C
COzMe
2. p ~ ; q $ t t b ; ~ ~ ; ( p H 7) t-Bu 3. MeOH ,pTsOH ,20"C overnight Pastor, I.M.; Yus. M_ Tetrahedron Lett., 2001, 42, 1029. m S i M e 3
58%
, Sc(OTf)3
PhCHO
t
90%
CH2Clz,rt , 5 h Ph Yadav..;Suhba Reddy, B.V.; Srihari, P. Synlerr, 2001, 673. 1. TMSOTf, CI12CI, -78°C SiMqPh
. .
2. aq NaOH
-0 HoJ%,o,
Melllll~~~
81% (83: 17 c k t r a n s ) Iwanami, T.; Yamamoto, A.; fio. Y, Synlett, 2001, 1042.
COzEt
Et02CCIf0, 1% Pd(MeCN)ZClz
*
D C M , r t , 18h Hao, J.; Taktak, S.; Aikawa, K.; Yusa, Y.; Hatano, M.;
Mdan$J-
96% H Synlett, 2001, 1443.
PhCIIO ,SnClz, NCS CHzClz, -60°C , 3 9 h
L
Mdsuvdma.; , , . Saeki, K.; Horiguchi, S.; Kurusu, Y. Synlett, 2001, 1802.
P 74%
h
35
Alcohols from Aldehydes
Section 34B
OBn
1. Cp&rC& ,BuLi
c-
2. PhCHO
96% (86: 14 antixyn) Tetruhedron Lett., 2001, 42, 1677.
85%
Takernoto.; Anzai, M.; Yanada, R.; Fujii, N.; Ohno, H.; Ihuka, T. Tetruhedron Lett., 2001, 42, 1725.
1. PhCHO
OEt
C02Et
BIIj*THF, CH2C12,-78°C
Hillier, M.C.;
4
a 0
q+ 88%
2. (Et0)2POCI12C02Et, 2 eq NaH THF,-78"C + rt . Tetruhedron Lett., 2001, 42, 5145.
NhC15, B I $ether, ~ I -78°C W
*
or1
Ph
(c-C6111I)2BCI,hexane , rt
1) 63%
-1
Ph 2,6-lutidine, 12 h G.W,; Wu, 2.;Ju, Y. Tetruhedron Lett., 2001, 57, 1663. PhBr , cat Pd(OAc),/PPh3
Bu-CH0
OH
Ph
(3 Andrade.; Azevedo, N.R.Tetruhedron Lett., 2001, 42, 6473. PhCI-I0
87~59%
Cs2C03 ,o-xylene , 3 h 1GOY! Terao, Y.; Kametani, Y.; Wakui, 11.; Satoh, T.; Miura. M.; Nomura, M. Tctruhedron, 2001, 57, 5967.
75%
c-GH11
Compendium of Organic Synthetic Methods, Vol 11
36
Section 3 4 3
Jdoh. T.-P,; Tan, K.-T.; Yang, J.-Y.; Xiang, C.-L. Tetruhedron Lett., 2001, 42, 8701
1
Nocentini, T. Tetruhedron Lett., 2001, 42, 4557.
1
&Bf
PhCHO
, Mn*
*
THF-hexane Kakiya, H.; Nishimae, S.; Shinokubo, H.; C
O
PhCHO
NH4C1
Ph
Tetruhedron, 2001, 57, 2365.
60%
Et,Zn ,hexane ,0°C
91%(97% ee)
chiral leucine derivative
Kawana
82%
i 1. PhCIIO, 2 eq TiCl(Oi-Pr)3 acetophenone ,20"C
L
2.
Pastor, I.M.;
Tetruhedron, 2001, 57, 8807.
Ph
u; Mitsuie, T.; Miki, M.; Sakamoto, T.; Nishitani, K. Tetrahedron, 2000, 56, 175. )2BC1 ,NEt3
PhCI-IO
*
2. H,O
P
an h
b
75%
G.W.; Wu, Z.; Trotman, S.E.; Gao, X. Org. Lett., 2000, 2, 255.
2
PhB(OH)2, DME/II20 ,50"C Rh(Xac)(we)z, P(t-Bu),
Ueda, M.;
J. Org. Chem., 2000, 65, 4450.
*
99%
Section 34B
Alcohols from Aldehydes
C1
37
PhCHO ,DMF ,Clclz
c1
Baati, R.;
.
1
'
73% (56:44) J. Org. Chpnz., 2000, 65, 1235.
JJPh
5% Pd(OAc), ,PhOII , 10% PPh3, rt
-
PhCHO, 2 eq BEt, , hexane/THF, 27 h Kimura, M.; Tomizawa, T.; IIorino, Y.; Tanaka, S.; m Tetruhedron Lttt., 2000, 41, 3627. SiCI,
Phff I 0
u
or4
I
, DMF, 0.2 h I
5% AgOTf
Eu-
78%
. Y.
; Voigtlinder, D. Synthesis, 2000, 959.
BF,- K+
BF,*OEt,, -78"C, 15 min
Ph
92%
-& /
OZN
OZN Batev. LA: Thadani, A.N.; Smil, D.V.; Lough, A.J. Synthesis, 2000, 990.
PhCIIO , Ni(dppe)Brz/Zn TIIF, 75°C Keck. G.E.; Wager, C.A. Org. Irtt., 2000, 2, 2307.
M 10 e-
93%
\ / 91%
Br , I n , D M F , r t
PhC€IO
b. F A ; Prahhudas, B. Tetrulzcdron, 2000, 56, 7595.
78% (92:s syn:anti)
Compendium of Organic Synthetic Methods, Vol 11
38
mBr , Sh/KF/HzO
PhCIIO
w
qumt
Ph
Li, L.-H.; i 3 a d . X . Tetruhedron Lett., 2000, 41, 5009.
mBr ,Cd,aqDMF
PhCHO
51%
Ph Synth. Commun., 2000, 30, 3517.
Zheng, Y.; Bao, W.;
O -H
Section 34B
1. TMSCl-NaI , MeCN, rt 2. Bio
Ge -
3. PhCHO Miyoshi, N.; Nishio, M.; Murakami, S.; Furuma, T.; Bull. Chem. Soc. Jpn., 2000, 73, 689.
l.
c-
*
68%
Ph
:;z:;:KyoM TMSCl , 6 h
96%
2. H,O Ph
OHC Kurohoshi, M.; Tanaka, M.; Kishimoto, S.; Goto, K.; Mochizuki, M.; Tetruhedron Lett., 2000, 41, 81. CHO
m
BrACOzEt
In,TIIF,rt,3h CozEt 95% ultrasound Lee.; Bang, K.; Lee, K.; Sung, S.-y.; Chang, S. Synth. Commun., 2001, 31, 3781. SiMe3
PhCHO
,YbC13, MeNNq
-u Ph
Fang, X.; Watkin, J.G.; Warner. B .P. Tetrahedron Lett., 2000, 41, 447. -snBu3
PhCHO
, 2 0 % ClCPh3 *
MqSiCl , CII2C12, rt Ph Chen. C.-T.; Chao, S.-D. J. Org. Chem., Z999, 64, 1090.
62%
65%
Section 34B
Alcohols from Aldehydes
39
0
II
0
I II
q
1. 2 eqBuLi
m
t.
"B-H N~s J (
2. PhCHO 77%
L OH
v. P, Emerschitz, T. Synth. Commun., 2001, 31, 961. I
, Mg/Iz
PhCIIO
t
q.0.1 NH4CI Zhang, W.-C.; J.i. C.-.I. J. Org. Chem., 1999, 64, 3230.
Ph
(allyl)2SnBr;?,HzO PhCHO
95%
t.
Cban.; Yang, Y.; Li, C.J. J. Org.
Ph Chem., 1999, 64, 4452. Ph
+ -
IFh BF4
\ /
Ma-(=)-
Chen, D.-W.; QchmJL . ' '
-
PhCHO , CC12
-
60%
0.1% NiC12, CC12
I
Ph A
O
Marx, A,;
A
I
B
~ , DCM, -78°C ~
s b
P~
10%(4-Br-2,6-di-t-Bu-phenoxyhAlMe Ph
Synlett, 1999, 584.
20%
c 93%
OH
Taylor. R.E.; Ciavani, J.P. Org. Lxtt., 1999, 1, 467. CHO
I
OMe
J. 01-8. Chem., 1999, 64, 6804.
Br
Ph
+
PhzCHOH
DMF, 25"C, 5 h
75 %
~
40
Section 34B
Compendium of Organic Synthetic Methods, Vol 11
OH
SnBu3
1 y
3qDMF,SnC14,12h -78°Crt Luo, M.; Iwahuchi, Y.;
Synlett, 1999, 1109.
PhCHO NaI , DMI , Sn12, , H,OTBN ,60"C ,47 h
*
OH
88%
++
Ph
(82
Masuvama.; Ito, T.; Tachi, K.; Ito, A.; Kurusu, Y. Chenz. Comntun., 1999,
*
0.1 Bu3SnH , 05 PhSiH3 AIBN ,PhH , 2 eq EtOII
Ph
*
HOs
p
h
1) 85%
(1.2
Hays, D.S.; Eu. (3.6Tetruhedron, 1999, 55, 8815.
79%
81%
Ph MeCN , 12 1120, It Iwai, 1.;Sugano, M. Tetruhedron, I999, 55, 7499. h
CI ro
''+6
, l o % Sc(OTQ
PhCI-I0
'I.;
I
+
l-butyl-3-mthylimidazolium Ph tetrafluomhorite (ionk liquid) . Chem. Commun., 1999, 1431.
.
Mivama.
18) 76%
126.
OH
(C€12=CHCI-12)4Sn
PhCHO
Ph
Loh. T.-P.; Xu, J. Tctmheriron Lett., 1999, 40, 2431.
PhCHO
(CII2=CHCII2)2Hg, 1120
80%
w
Chan.; Yang, Y. Tetmhedmn k t t . , 1999, 40, 3863.
Ph
Section 34B
Alcohols from Aldehydes
41
PhCIIO , AgOTf, CHzCl2 0°C , 15 min
WSEb C
Chataigner, I.; Piarulli, U.;
CSIITi-CHO
'
* E
1.2 Bu3sn-B~
h
85%
O
4A-JJ
BF3-K*
=+ SnBu,
c5k11 1
73% (77:23 E:Z)
Lee. AS.-Y,; Wu, C.-W. Tetruhedron, 1999,55, 12531.
Me
98:2 dr) Batev.;Thadani, A.N.; Smil, D.V. Tetruhedron Lett., 1999,40, 4289. Bu3SnH, BEt, ,02
I
toluene, -78°C
4
0°C
O r m Devin, P.; Fensterhacnk, L.; Malacria. M. Tetrahedron Lett., 1999,40, 5511. PhCHO , BEt, , hexandTHF ,rt
-
INi(x=)21,4 h
87%
Ph
90% (1: 15 Jyn:unti) Kimura, M.; Fujimatsu, H.; Ezoe, A.; Shibata, K.; Shimizu, M.; Matsumoto, S.; Angew. Chena., Int. Ed., 1999,38, 397.
2
PhCIIO , 3.3 ey ATPH 2.3 eq LIMP, -78°C w C 0 2 M e
toluenefilI F ATPH = tri(2,6-diphenylphenoxy)aluminum
%A/ Ph
97% Saito, S.; Shiozawa, M.; mote. I t Angew. Chrnt. Int. Ed., 1999,38, 1769.
C02Me
Compendium of Organic Synthetic Methods, Vol 11
42
Section 37
,catIn,Mn/TMSCl H,O, I d
1. &Br
PhCIIO
71%
/
2. HzO
Ph
AueC.;Luhin-Germain, N.; Thiaw-Woaye, A. Tetmhedron Lett., 1999, 40, 9245. ,Ga,KI
1. B-r
PhCIiO
THF , LiCl ,reflux
*Ph+
2. HzO 94% (54:46 Jynranti) Han, Y.; Chi, Z.; Huanp. Y. -ZLSynth. Commun., 1999, 2Y, 1287. SiMe3
, 5 min
dE
fiSiMe3 * MqSi TiCb , DCM ,-60°C Princet, B.; Anselme, G.; pornet. .I. Synth. Comniun., 1999, 2Y, 3329.
EtCHO
54%
REVIEWS: "Catalytic Asymmetric Organic Zinc Addition to Carbonyl Compounds", Chem. Rev., 2001, 101, 757.
SECTION 35:
u; Yu, H.-B.
ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLS
No examples of the reaction RR1 .-+ ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactions of the type RH 4 ROH (R = alkyl or aryl) see Section 41 (Alcohols and Phenols from IIydrides).
SECTION 36: ALCOHOLS AND THIOLS FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 37: ALCOHOLS AND THIOIS FROM AMINES 1. B uLi ,THF ,-45°C 2. H+ Me
Me
3. NaBH, , MtOII Bu Shieoya, Y.; Nagaoka, Y.; Yamada, K.4. J. Org. Chem., 2001, 66, 7051
74%
Alcohols from Esters
Section 38
43
'5
diethylene glycol, KOH 210"C, 12 h NH 2 Rahman, S.M.A.; Ohno, H.; N-
J
Ph
76%
3eq
OH
L \
Tetruherlron Len.,2001, 42, 8007. 2 eqIn, H20
Ph
. . ;-
*
ABr
85%
Ph
Winotapan, C.; Shinada, T.; Ohfune, Y. Tetruhedron Lett., 2001, 42, 9073.
SECTION 38: ALCOHOLS AND THIOLS FROM ESTERS NaBH4-LiC1, 5 min
* PhCH,OH 75% microwaves Jhg. J . - C Liu, B.; Dai, L.; Yang, X.-L.; Tu, S . 4 . Synth. Commun., 2001, 31, 1875. PhCO,Et
Q-M 0
Ph Kauch, M.; Hoppe. PhOAc
1. BuLi, TMEDA 2. TMSCl ~
97%
3.2MHCl Ph
D, Cun. J . Chem., 2001, 79,1736. sulfiiiatod bomhydride exchange resin
*
MeOI1,25"C, 10 min Bandcar. B.P.; Kamble, V.T. J. Chern. Rex (S), 2001, 54.
PhoH
94%
MeTi(Oi-Pr)3 , 4 eq EtMgBr
THF ,0°C Quan, L.G.;
Org. Lett., 2001, 3, 2745.
T i C b E n , C€I2CI2
e PhSH 87% 0°C , r t Jin, C.K.; Jeong, H.J.; Kim, M.K.; Kim, J.Y.; Yoon, Y.-J.; J.ee. S.-G. Syntett, 2001, 1956.
PhSAc
Compendium of Organic Synthetic Methods, Vol 11
44
Section 38
EtMgCl , Ti(Oi-Pr)4
OH
THF ,r t
81%
Lee, J.C.; Sung, M.J.; Cha. J.K. Tetmhedron Lett., 2001, 42, 2059. T i c k ,Li , THF , rt OTs
18 h
* +OH
Synthesis, 2000, 1575.
&y&A&
Zn(BH4)2 ,EtMgBr
C$ ,9-COzMe
-
1
THF, rt GI49 Balasuhramanian, S.; Nair. M.G. Synth. Contnzun., 2000, 30, 313.
.
B
n
\ e /O
O
T
Reddy, G.S.; Mohan, G.H.;
s
CeC13-7 HzO-NaI MeCN,6h '
* B
75%
76%
Et
n
\O O/
O
H
95%
Synth. Conintun., 2000, 30, 3829.
Ph2SiH2, cat PPh3, TI-IF, rt
cfi 19COZEt
98%
t Cfi19CHzOII 10% [ R h C l ( ~ ~ d ) ] 72 z, h Ohta.;Kamiya, M.; Kusui, K.; Michihata, T.; Nobutomo, M.; Furukawa, I. Tetruhedron Lc.tt., 1999, 40, 6963.
K S
COzMe
5 eq Mg , MtQH reflux, 30 inin
011
79%
Rho, H.-S.; KO, B.-S. Synth. Continun., 1999, ZY, 2875. 5 ~NaBII4,IIMF
MtQ &Coz*
MeOH, reflux , 1 h *Me0
Zanka.; Ohmori, H.; Okamoto, T. Synlcitt, 1999, 1636.
c&ori 98%
Section 39
Alcohols from Ethers
SECTION 39:
45
ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS Et3Al, 5% Pl'h3, toluene
*
D
O
rt,ld
H '%It
99%
Et
Schneider. C.; Brauner, .I. Eur. J. Org. Cheni., 2001, 4445.
NaN3, € 1 2 0 , AlCh IIOZC
pH4,3O0C,3.5h
u-f r
.c
H02C
J+
99% N3
h p g g l l ~ F.: . Pizzo, F.; Vaccaro, L. Tetruhedron Lett., 2001, 42, 113 1.
I2 ,CII2Cl2, 10°C , 1 h
%,,,
Vatele.
92%
J.-M. Synlctt, 2001, 1989.
(90 v. J.S.; Arijaneyulu, S.; Ahmed, Md.M.; Subha Reddy, B.V. Tetruhedron Lett., 2001, 42, 2557.
o\
10) 90%
1.4e q M e 3 N ,1 eq H 2 0 DCM ,-2O"C, I h
0 2.H30' Wipf. P.; Rihe, S. Org. Lett., 2001, 3, 1503.
2 qAlEt3, I d imidazolium salt catalyst
*
uEt 76%
1%
Zhou, H.; Campbell, B.J.; &uv . en. S . T Org. Lett., 2001, 3, 2229.
"'OH
Compendium of Organic Synthetic Methods, Vol 11
46
Section 39
1. Li, 5% DTBB ,TI-IF 2. ZnBr2, THF 3 . 5 % Pd(PPh3),, THF, 60°C 4. HCl-HZ0 77%
Gomis, J. Tetrahedron Lett., 2002, 42, 5721.
NaN3 , rt , 6 h phase transfer ammonium PhL resin
Ph
0
-k
H
(9 1 Mahdavi, II. Tetruhedron Lett., 2002, 42, 8721.
;-
1. BuLi, DCM 2 . 3 eq Me3Al, 0°C + It
-p -
9) 95%
96% ( > 9 7 : 0 13-:1,2diol)
'
OBn
N3
Ph
OB n Sasaki, M.; Tanino, K.; J'vlivashita. M, Org. Ldt., 2002, 3, 1765.
Go
2.5 eq -78°C BuLi,+THF, rt 1 h
-JII 0
w 1 1
D M ; Stent, M.A.H.; Wilson, F.X. Org. Lxtf., 2001, 3, 3401.
C5H1 1
Et3AI, 5% P(NMed3 toluene ,rt , 1 d
Schneider.;Brauner, J. Tetruhedron Lett., 2000, 41, 3043.
Ylq
ye --
5
Me
5% Pd(PPh3)4, MezNH-BH3 Lc
3eqAcOH,DCM,rt,15min
Me
C02Bn 92% David, H.; Dupuis, L.; Guillerez, M.-G.; Guihe. F. Tetrahedron Lett., 2000, 41, 3335. CO$n
Section 39
Bt-0
Alcohols from Ethers
Ph
41
1.2.2eq BuLi
Ph%OH
2. HZO
ON:
v. A . R ; Fang, Y. Heterocycles, 2000, 53, 1783. 1. MgSiN, ,Bu4NC1 , neat
*
2. P-TsOH, MeOII
. ,
40%
Bu
Synlett, 2000, 1840.
89%
% ",,
BF3*OEt2,DCM
aOv
75%
Prestat, G . ; Baylon, C.; &&. M.-P.:
/
solid phase microwaves , DMF , 4 min
/
* H
Kumar.;Anjaneyulu, S.; Reddy, B.V.S.; Yadav, J.C. Synlett,
Noguchi, Y.; Yamada, T.; Uchiro, H.;
O
2000, 1129.
W
92%
(95 5) 84% Tetrahedron Lett., 2000, 41, 7493, 7499.
48
Compendium of Organic Synthetic Methods, Vol 11
ON3
1. Th4SN3 , Cr-salen catalyst
[emim] SbF6,20°C
2. CSA , MeOH * "'~8Il#OH Sonr.; Oh, C.R.; Roh, E.J.; Choo, D.J. Chem. Coinmun., 2000, 1743.
(90 oor. N,; Kazemi, F. Synth. Continun., 199Y, 29, SGl. 2% TiQ(OTf), MtOH
P h it^^^
Section 39
0°C , 5 min
75% (87% ee)
10) 93%
-
MeO 95% (89% ee)
Iranpoor, N.; Zeynizadeh, B. Syntlz. Cornniun., Z999, 2Y, 1017. 1 . 2 q A l C 1 3 , 2 q NaI
Ph-OMe ci.
2.5% Na2S203 Asghari, J. Synth. Cornniun., 1999, 29, 973.
m;
*
Ph-OH
98%
-
Li naphthalenide , THF -78°C rt , 10min 0
Jankowska, R.; Mhehe, G.-L.;
b. H. -J, Cheiii. Continun., 1999, 1581.
78%
1 . 2 q i-PrSNa, DMF 1GO"C , 4 h P
h
\ e /S
S
M
e
2. aq HCI
Pinchart, A,; Dallaire, C.; Van Bierheek, A.;
93% Tetmhedron Lett., 1999, 40, 5479.
1. Hg(OAc)z, TIIF/II20 2. NaBHdaq K2C03
OH 62% Crouch.; Mehlmann, J.F.; Herh, B.R.; Mitten, J.V.; Dai. G , Synthesis, Z999, 559.
Section 40
Alcohols from Halides
x
I
I
A/
Ph
49
2. l.K”’lrz HzO
-
€
SiMe,
1
I HO/,
4
Ph
Ph
m . Geng, ;F. Org. Lett., Z999, I, 1115. 1
21%
I.
Additional examples of ether cleavages may he found in Section 45A (Protection of Alcohols and Thiols).
SECTION 40:
ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES 1. Mn*, TIIF, rt 2. PhCHO ,THF
Ph-OMS
*
1. BEt3, DCC , DCE -50°C. syringe pump
2. M e o r r ; ~ q ~
I
Kihara, N.; Ollivier, C.;
*
2. EtCHO
82%
+OPh
Org. Z*.rf., 1999, 1, 1419.
1. B u N g L i ,TIIF,U’C, 0.5 h
PhBr
72%
OH
othm ekctrophiles can he used Kim, S.-H.; Rieke. R.D. Tetrahedron Lett., Z999, 40, 493 1.
oir
9”
t
Ph Inoue, A,; Kitagawa, K.; Shinokubo, H.; Qshima. K. J. Org. Client., 2001, 66, 4333. 1. FSM-16 , N a I , hv , acetone, r t , 1d
PhA
v
B
r 2.FSM-16, CsI , h v , i-PrzO, 12 h
t
wcrro
Ph
Itoh. A.; Kodama, T.; Inagaki, S.; Masaki, Y. Org, Lett., 2001, 3, 2653.
86x8 1%
50
Section 41
Compendium of Organic Synthetic Methods, Vol 11
SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES
90% conversion
u; Feiten, H.-J.; Chang, D.; Duetz, W.A.; van Beilen, J.B.; Witholt, B. J. Org. Chem., 2001, 66, 8424.
5
HO cultured cells of Gocsypium hirsutum I1II1II1I
11l111111
Hamada.;Tanaka, T.; Furuya, T.; Takahata, H.;Nemoto, II.
72%
Tetruhedron Lctt., 2001, 42, 909.
’)96% ee ,S)
Weui, Z.-L.;
Lt. Z.-Y.: Lin. G .-OLTctruhedron Asymm., 2001, 12, 225.
A 0
y
i-PrOH ,20"C, 4 h
Ph
3% [
Bied, C.; m
u
*
NHCO Nf Ii-Pr
I"'
N Hz
/0.5 KuCLz@-cymeiw)]
. J.J.E.; Man, M.W.C. Tetruhcclron Asymm., 2001, 12, 329. i-PrNEtPh*BH3,THF, 25°C
Ph~
75% (63%e e , R)
Ph
s o z T o l
(3; .N
n' \
Me
Cho.; Kim, D.J. Tetruhedron Asymm. 2001, 12, 2043.
*
QI I I
&S q T o l
Ph
98% (>W%ee ,S)
56
Section 42A
Compendium of Organic Synthetic Methods, Vol 11
Curvuluriu luncltu , 10 h Phj i S O 2 P h
QH -
+A
SOzPh 90% (87% ee ,S)
Ph
Gotor, V.; Reholledo.; Liz, R. Tetruhdron Asyrnm., 2001, 12, 513. carhonyl rtxuctase S1 C02Et quant (>99% ee ,S) Yasohara. Y .; Kizaki, N.; Hasegawa, J.; Wada, M.; Kataoka, M.; Shimizu, S. Tetruhedron Asynim. 200I, 12, 1713.
A
=A
BH3-SMe,, squaric acid ligand
95% (95% e e , R) Ph toluene, 50°C Ph Zhang, J.; Zhou, €L-B.; Lii,S.-M.; Luo, M.-M.; Xie. R.-G.; Choi, M.C.K.; Zhou, Z.-Y.; Chan, A.S.C.; Yang, T.-K. Tetrahedron Asymiiz. 2001, 12, 1907.
A A
P h S i H ? , cat [Kh)cod)ClI2 , neat
Ph
cyclic ke timine ligand
-A Ph
v. Keyserlingk, N.G.; Martens. J. Tetruhedron A.ryinm. 2001, 12, 2213.
86% (54% ee)
-A
BH3-oxazahoiulidine , amino-alcohol ligand
92% (74% ee ,S)
THF Ph Feng, Y.; Hang, .f.-F. Tetruhedron Asytiinz., 20UZ. 12, 2323.
Ph
*A
1%chiral Ru compkx , i - M I I
Ph
Lutsenko, S.;
4
Ph
1
micmwaves , 9 min Ph Tetruhedron Asyntm. 2001, 12, 2529.
90% (82%e e , R)
QH Ywuufuzyiriujurinosu IF0 10896 I d
-
*P
h
q
91% (>99% ee,S)
OH 0 1I Tsujigami, T.; Sugai, T.; Ohta. 11. Tetrulrerlron Asynrm. 2001, 12, 2543.
Section 42A
0
I1
Ph Lin, Y.-M.; Fu, I.-P.;
Alcohols from Ketones
BH,-SMe,, DCM , 10% Al(Oi-Prh 21% hinaphthyl ligand ,0.5 h
57
PH - /Z
95% (71% e e , ~ )
Ph
m.B.-1. Tetruhedron Asymni. 2001, 12, 3217.
1
1. PhSiH3, CuF,/S-BINAP toluene , rt , 2 h
79% (78% ee, S) Ph Sirol, S.; Couriiiarcel, J.; Mostefai, N.; R l d n t . O r g . Lett. 2001, 3, 4111. Ph
A
Ph
2. ay HCI
i-Pa11 , cat RuClz (PPh3),
20" , tetramine ligand , 2d
-
A
44% conversion 44%e
Ph
Marson.;Schwarz, I. Tetruhetlron Intt., 2000, 41, 8995.
S,S-Ru catalyst, 27°C:
(9S%ee,S)
*
-f
HCOOII , NEt, , 12 h
0 OH Okano, K.; Murata, K.; M y a . T. Tetrahedron L a . , 2000, 41, 9277.
A c&.',
NaBII4 / MqSiCI , TIIF, 25°C
Ph
10%
PI1
-
-1
98% (96%e e , R )
Ph
HO Jim:. B.; Feng, Y.; Zheng, J. Tetruherlron Lett., 2000, 41, 10281.
A A
oxazohorolidine catalyst , TIIF
Ph BH,*SMq, rt Santhi, V.; Rao, J.M. Synth. Cnmntun., 2000, 30, 4329.
Ph
ofr
* A
chiral P-diamine , BH3*'I'€IF , THF -15"C, 2 h
Sato, S.; Watanabe, H. Chent.Lett., 2000, 990.
88% (70% ee)
Ph
* A Ph
88% (92%ee, R )
58
Compendium of Organic Synthetic Methods, Vol 11
Section 42A
cat [Rh(cod)z] BF4 , Ph2Si€Iz
chiral his-phosphine , THF , 4 0 ° C
Kuwano, R.; ; Shirai, J.; Takahashi, M.; Jto. Bull. Chem. SOC. Jpn., 2000, 73, 485. BH3.THF ,proline, T H F
*
rt , 10min
90% (91% ee)
Y,
1
quant(85%ee)
Ph TeodomviC, A.V.; Joksovik, M.T.,.; Konstantinovie, S.K.; Mojsilovie; Mihailovie, M.L. Monut. Chem., 2000, 131, 91.
'k
Bakers yeast, 1 d
=
Ph
Ph
75%(97%ee)
N-OMe N-OMe Kreutz, O.C.; Segura, R.C.M.; Rodiigues, J.A.R.;Moran. P.J& . .Terruhedron Asynttn., 2000, 11, 2107.
A
Geotrichutii cunrlitlr~rilimmobilized resting cells
* A A . -A
51% (>99% ee ,S)
. . super cr itica 1 CO, Ph Ph Mdtslada.;Harada, T.; Nakamura, K. Chent. Conimun., 2000, 1367.
1
ph
Ru catalyst, Hz , I-PiOH t-BuOK
*
Ph
9 8 % ~
. . Org. Lett., 2000, 2, 4173. Burk,;Hems, W.; Henberg, D.; Malan, C.; h t t i -GtraSLL&
A
aryl oxazaphospholidine oxide
BII3 ,THF Ph Ph Brunel. J.M.; Legrand, 0.;Buono. G. Eur. J. Orb. Chem., 2000, 3313.
95% (32% ee)
Cutvuluriu lunutu CECT 21 130 phosphate buffer, pH 6 , MeCN Dehli, J.R.; &&or. V. Tetruherlron A~pittii.,2000, 11, 3693.
55% (96% e e , S )
Section 42A
Alcohols from Ketones
59
OH
--
Synechococcus sp FCC7942 9d
51% (98% ee ,S) Yamanaka, R.; Tohi, K.; IIamada, €1. Tetruhedron Lett., 2000, 41, 6799.
Nakam-;
chiral perfluoro s a k n ligand ,70"C [Ir(cod)Cl]2 , i-PiOH , D- 100, KOH
0
II
A
OH
I
2d Ph Maillard, D.; Nguefack, C.; Pozzi, G.; Quici, S.; Valadb, B.; Tetruherlron Asynzm., 2000, 1 1 , 2887.
A
chiral oxazahoroline ,BHj.SMe2 1XF,rt, 2 h
Ph
I\
.r
Ph
*A Ph
Santhi, V.; h o . J.W Tetruherlron Asymnz., 2000, 11, 3553.
91%(56%ee)
94% (93% ee)
L
Hz (40 bar) , cat diamine-BINAP L
C
0
2
M
e
MLOH, S O T , 14 h
COzMe
quant (99% ee)
ter Halle, R.; Colasson, B.; Schulz, E.; Spagnol, M.; Tetruhedron Lrtt., 2000, 41, 643. H
A
4
2 BI-13 , THF Ph Jones.; Atherton, J.C.C. Tetruhedron Asynim., 2000, 11, 4543. Ph
>95% (84% ee)
Ceotrichuni canriiriuni I F 0 4597 Amherlite XAD-7 83% (94% e e , S) Nakamura. K.; Fujii, M.; Ida, Y. J. Cheni. Soc., Perkin Truns. I, 2000, 3205.
60
A
*x
0.1 chiral diamine ,BH3*THF
THF ,rt
Ph Sato, S.; Watanahe, H.;
A
Ph Tetruhedron Asynirti., 2000, 11, 4329.
'
40 hw H2, i-PaWt-BuOK
chiral polymer catalyst S O T , 18 h ter Ilalle, R.; Schulz, E.; Spagnol, M.;
.
.
Cr(L-His)+ , DMF-€120
rt ,pH 6.5
0
Hajdu, C.; Jekij, J.; IRvai, A,; Tetruherlron Lett., 1999, 40,1373.
A
Ph Synlett, 2000, 680.
-
ph?
Ptk fI2N
OH
33% (36% e e , S)
; Zucchi, C.
2 eq LiBH4/Ni12, TIIF
Ph
88% (87% ee)
quant (68% ee)
Ph
;-
Section 42A
Compendium of Organic Synthetic Methods, Vol 11
*
Ph
H
Ir:
Ph
OII
94% ee
Molvinger, K.; Lopez, M.; Court. .I, Tetruhedron L t t . , 1999, 40,8375.
A A
CpRhCl(chird diamine) , 12 h
Ph Murata, K.;
Ph
*
i-PrOH ,t-B uOK ,30"C J. Org. Chent., 1999, 64,21XG.
9-- H
A
92% (94% e e , R)
Ph
10,l l-dihydrocinchonidine ,AcOH 1% PdlAIZQ , 17"C, 5.8 h~ H2 CO&t
Phd a z E t
LeBlond, C.; Wang, J.; Liu, J.; Andrews, A.T.; Sun. Y.-K, J. Am. Chem. Soc., 1999, 121, 4020.
1%
>'\B-Me Me0 ' 0
BH,*SM%, THF, rt
*
91%ee,R
1
Ph Puijaner, C.; Vidal-Ferran, A.; Moyano, A.; perichs. M.A.; Riera, A. J. Org. Cherir., 1999, 64,7902.
>99%(96%ee)
Section 42A
Alcohols from Ketones
jl.*
+ a
bakers yeasf, petm 4 0 6 0
Ph
4"C,7d
61
P[I/..
-
Ph
cinchona rmdifkd Pt catalyst & 0 3 , H 2 , 60 b a r , 25°C
++
AcOH , MeOH OMe OMe Studer. M.; Burkhardt, S.; Blaser, H.-U. Chcnt. Conintun., 1999, 1727.
Ph
Bolm.;Derrien, N.;
PhL
C
O
z
59%
; Ten, A.; Trewhella, M.A. Org. k t t . , 1999, 1, 1879.
Florey, P.;
-
BI-I3*SMq , THF, It 10%dendritic chiral catalyst
96% ee
QH
A
Ph
80%(89%ee)
Seger, A. Chern. Cornmun., 1999, 2087. 1. DlP-Cl, NEt,, 1'HF
H
2. aq OH; aqH+
- Lmz Ph
DIP-C1 = B-chloro diisopinocampheylhor~ne
87% (98% ee)
u; Zhao, C.; Pierce, M.E.; Fortunak, J.M. Tetrulzcdron Asymm., 1999, 10,225.
A
*
92% (73% e e ,S )
Ph
BH3*SMq, toluene, 25°C Yane.;Lee, D.-S. Tetruherlron Asyrnnt., 1999, 10, 405.
Tommasino. M.L.; Thomazeau, C.; Touchud, F.; Tetruherlron Asymrn., 1999, 10, 1813.
ji
*x
10%c h i d pyriulidine alcohol
Ph 12% M(OEt), , BII3-SMez Ph Yanagi, T.; Kikuchi, K.; Takeuchi, 11.; Ishikawa, T.; Nishimura, T.; Chem. k,tt., 1999, 1203.
quant (97.5% ee)
a
62
Section 42A
Compendium of Organic Synthetic Methods, Vol 11
A
20%
-
&IM'
BH
x
, BH3-SMe2t
91% ee
Ph THF , S O T Ph Li, X.; Yeune. C .-h ... Chm. , . A S.C.: Yanp T.-K. Tetruhedron Asymm., 1999, 10, 759.
1
*
95%991%ee)
zpie -
chiral G a complex Ph Ford, A.; W o o d w u Angew. Chmi., Int. Ed., 1999, 38, 335.
1.0.1 Ph&OM.
N-4
-
OH t
ph/YoMe
2. PhNEt,*BH,, THF , 25°C OMe OMe Cho. B.T.; Chun, Y.S. J. Clzem. Sor., Perkin Truns. I , 1999, 2095.
..
OH ---
BH,.OEt,, LR, THF Ph
93% (95%ee)
quant (95% ee)
P h A ,
Me Ford, A.; Woodward, S. Synih. Cornmun., 1999, 29, 189.
Cnlmes. M.; Escale, I;. Synth. Cornmiin., 1999, 29, 1341.
YKER-1 enzyme NAD PI I 0
- _.
QH
Y3H7 0
92% (>99%ee , S)
Kawal.;Hida, K.; Tsujimoto, M.; Kondo, S.4.; Kitano, K.; Nakamura, K.;Ohno, A. Bull. Chem. Soc. Jpn., 1999, 72, 99.
Section 42A
Alcohols from Ketones
L ~ B I ITIIF, ~, 2
0
63
~
chiral Lewis acid
Nozaki.;Kohori, K.; Uemura, T.; Tsubumi, T.; Takaya, H.; Hiyama, T. Bull. Chem. SOC.Jpn., 1999, 72, 1109.
NON-ASYMMETRIC REDUCTION
Iph
NiClz , N&H4
*
88%
Ph THF , r t , 15 min Khurdnd.; , . Chauhan, S. Synth. Conitnun., 2001, 31, 3485. Ph hP’
0-o
eoH
aq TiC13 , NH3, MeOH
*
0°C
68%
Clerici, A.; Pastori, N.; P o r t a . E i i r . J. Org. Client., 2001, 2235.
Bae, W.; Lee, S.H.; Jung, Y.J.; Yoon, C.-O.M.; yoon. C& Tetruhedron LL’tt., 2001, 42, 2137.
t
-
B
u
O
O
PhSiIi, , M n ( d ~ m ) ~* t DCM , i-PiOH,O2 ,rt
-
II
A
Ph
0.2% RuC12(I’Ph3X ,2.4% NaOII 0.4Yb(OTQ3, i-PiOI-I, reflux
*
l h
u
A
1-1, , 10% Pd/C-ethylenediamine
Ph
MeOH,3h
*
Tetruherlron, 2001, 57, 4781.
O
H
74%
xph
Ph Matsunaga, H.; Yoshioka, N.; u d d . T. Tetrahedron LElt., 200I, 42, 8857.
..
O
98% (14:l trans:cis)
Magnus. P,; Fielding, M.R. Tetruhedron Lett., 2001, 42, 6633. 0
B
Ph
96%
64
Compendium of Organic Synthetic Methods, Vol 11
Section 42A
MedI Mqo @ @ L ~ A ~ H ( O ? - B THF U)~,
N
'zbc
t
J
-78"Cd
80%
18°C
N-J
BZ'
IIuang, H.-L.; Wang, C.-L.J. Tetruherlron Lett., 2001, 42, 1329.
Me rulius t~r?m~Unsus
MeO
MLO
61%
c1 c1 Petra, D.G.I.; Field, J.A.; Schipper, D.; Wignherg, J.B.P.A.; Karner, P.C.J.; Reek, J.N.H.; van Leeuven, P.W.N.M.; Wever, R.; Schoemaker, H.E. Tetruhedron Asymm.. 2001, 12, 1025.
;.A-
&
BH3oTHF ,THF, ~ f l u x
-6
\\,*\\\'\\
81% (>99.5% trans)
Cha.;Moon, S.J.; Park, J.H. .I. Org. Chcni., 2001, 66, 7514.
Ph
Ph
-
Lfi
1. FH3{P(C,H,,),)], toluene -78°C
It, 15 h
OH 2. aq H+ Ahernathy, C.D.; Cole, M.L.; Davies, A.J.;
*
Ph
-
quant
OH Tetruhedron Lett., 2000, 41, 7567.
Na2C03 , 13S"C, 12 h 5% Pd(0Ac)z ,2 eq KOAc
Ph
DMF
a
Quan, L.G.; Lamrani, M.; Yamamo
Ph Phukan, P.; &&&u-& '
69% J . Aria. Chent. Soc., 2000, 122, 4827.
inacmcyclic Ni catalyst
*
KOH ,i-PIOH , 82°C Syntli. Corriinun., 2000, 30, 2401.
A
Ph
78%
Section 42A
Alcohols from Ketones
Po
Hayakawa, R.; Sahara, T.;
Bn\
'$
Ph
Tetrulzdron Lett., 2000, 41, 7939.
Ti(0i- Pr),
H;#::)
* Bn\
K-Selectride ,TIIF -100°C , 15 inin
OH
1
Np
c'. CPh Bn,
N
(> 100 O H . OH Tetruhodron Lett., 1999, 40, 593.
Lawson, E.C.; Zhang, H.-C.;
Ph
65
1 . 5 e q C ~ S i H , C I 1 2 C 1 21, 2 h
C
N-CIIO
,o"C-.
rt
1) 91%
-
Iwasaki, F.; Onomura, 0.;Mishima, K.; Maki, T.; Mntsumura. Y. Tetruherlron Lett., 1999, 40, 7507. 3 eq SmI2,2 eq H 2 0 0°C , 1 h k k . G E ; Wager, C.A.; Sell, T.; Wager,
*
96% (83:17 a n & ~ y n )
T.T.J. Org. Chenz., 1999, 64, 2172.
K( T ~ ~ PHBn ) ~ B,THF Trip = triisopmpylphenyl
85% (>99%cis)
Smith. K.; El-Hiti, G.A.; Hou, D.; DeBoos, G.A. J. Cheni. Soc., Perkin Truns. I, I999, 2807.
6G
Section 42B
Compendium of Organic Synthetic Methods, Vol 11
NaBH4, Si02 , hexane
2
0°C , 1 h Yakahe, S.; Firano. M.; Morimoto, T. Synth. Commun., 1999, 29, 295.
Ph
0
p h ~ c H @ ~
BuzSnH2-BusnFz, THF rt,2h
OH
0
+ IIMPA + LiI
89% 0% 0% 83% Moriuchi-Kawakami, T.; Matsuda, H.; Shihata, I.; Miyatake, M.; Suwa, T.; Bull. Chern. SOC.Jpn., 1999, 72, 465.
OH 94% (63:1 synzanti)
m o l r n . E.J.; Schulte 11, J.P. J. Org. Chem., 1999, 64, 2610. REVIEWS:
"Enantioselective Reductions hy Chirally Modified Alumino- and Borohydrides", Daverio, P.; Tetruliedron Asynim. 2001, 12, 2225.
SECTION 42B: ALKYLATION OF KETONES, FORMING ALCOHOLS Aldol reactions are listed in Section 330 (Ketone-Alcohol)
ASYMMETRIC ALKYLATION
LCN
Ph
Dehli, J.R.;
Cuivuluriu lurwtu EtOH
---
QH b
Tetruhedmn Asymm. 2001, 12, 1485.
P h / Y C N Et
69% (98%ee)
Section 42B
A
67
Alcohofs from Ketones
*A
Ira(cod),.hiral amino-alcohol sulfoxide
99% (65% ee) Ph Petra, D.G.I.; Kamer, P.C.J.; Spek, A.L.; Shoemaker, H.E.; van Leeuven, P.W.N.M. J. Org. Chenr., 2000, 65, 3010. Ph
A
HCOOIVNEG ,6O"C, Hz
0.25 [R~Cl~(p-cyrnene)]~, Hz , 0.7 h
2% chin1 amino-alcohol 2.5%i-ROK, I-PiOH Alonso, D.A.; Nordin, S.J.M.; Roth, P.; Tamai, T.; J. Org. Chent., 2000, 65, 31 16.
Ph
*A Ph
97% (94% ee)
..
(CIIZ=CHCI~~)~SII, DCM ,rt
R-B inal-Ti Ph Ph Casolari, S.; DAddario, D.; Tanliavini. . Org. k t f . , 1999, 1, 1061.
70% (55%ee)
NON-ASYMMETRIC ALKYLATION
+ 0.1 CUI (NO TMSC1,NOCuI (63% b e . P a ; Ahn, H.; Lee, K.; Sung, S.-y.; Kim, S. Tetruhedron ZAL,
/g
60%
-1 )
2001, 42, 37.
mBr ,Sin, THF
* I1% Ph rt ,20inin Ph Basu, M.K.; Banik. B.& Tetruhedron Lett., 2001, 42, 187,
Cdhezds.; . ,, Pereira, A.R.; Amey, A. Tetruhedron L.&t., 2001, 42, 6819.
80%
96%
68
Section 42B
Compendium of Organic Synthetic Methods, Vol 11
A
Ph Kamhle, R.M.;
Sn(CH2CH=CH2)4,DCE
10% CU(OTQ2,lOh
y I ' Ph
72%
m.V.K. Tetruhedron Lett., 2001, 42, 7525.
,TIIF,rt C&Ti(OPh), Tctruherlron Lett., 2001, 42, 8567.
Quan, L.G.;
&
9Me
63 %
0
/I
A
f P
N-Rn
S d , , acetone, THF , rt
-Bn
sqPh
*
OH
Yoda. H.; Ujihara, Y.; Takahe, K. Tetruhedron L.ett., 2001, 42, 9225.
A
Ph
1. H O C C I I Z B r , N d , Dy THF, HgC12, -14°C
2.H 2 0
+
Ph
-
Li, Z.; Jia, Y.; U o u . J, Synth. Conintun., 2000, 30, 2515.
ori
I Ph4
0, , pivaklehyde , MeCN, rt
Co salen complex , 8 h
0
k
II
*+ r \
Ph
Fernindez, I.; Pedro. J.E.; RosellB, A.L.; Ruiz, R.; Castro, I.; Ottenwaelder, X.; Eur. J. Org. Chern., 2001, 1235.
1. Tic& 2. MeMgC1-CeQ , ether M%N
3.II,O+
75%
,llllw~
MqN
85% (>98% de) Bartoli. G,; Bosco, M.; Marcantoni, E.; Massaccesi, M.; Rind&, S.; Sambri, L. Tetruhedron Lett., 2001, 42, 6093.
69
Alcohols from Ketones
Section 42B
S d z , cat NiI, , TIIF
OH
0
m.G.A.; Le Huirou, Y . ;Brown, G.A. J. Org. Cltem., 2002, 66, 4511.
a
0
04.
OH
1. M e %Me TiCb ,DCM
-78T , 15 rnin OMe 2. -78"C, 15 n i n ~
S
I
CqMe
I
B
~
+
CaMe
~
63% 20% Ghosh. A.K.; Kawahama, R.; Wink, D. Tetrahedron Lxtt., 2000, 41, 8425. 1 . TinI,(l>ME), , DME , .; Sharma, 17. Tc.trrihedron,2001, 57, 9343. 1 . THPOAc. 5% TBS-OTf EtCN , -7i(”C, 1.5 inin
2. 10% Et3N, -78”C, 5 inin
. Synthesis, 2001, 555.
* Ph-0THp 96%
78
Section 45A
Compendium of Organic Synthetic Methods, Vol 11
1.5eq A c 2 0 , MeCN , 25 inin Ph-OH
0.1 Bi(OTO3.x H2O Carrigan, M.D.; Freiherg, D.A.; Smith, R.C.; Zerth, H.M.; Syntltesis, 2001, 2001.
4'
b&n
82%
OH 60%
Org. Lett., 2001, 3, 2835.
AcOII , P 2 0 5 , S i 0 2 , rt
60%
u; C6H13011
c 88%
* ph4Ac solid state , 6 h Rafei, M.: Karimi, M.H. Synth. Comnnzun., 2001, 31, 771.
P h 4 H
A
Brio BnO
0
Kitov, P.I.; &,&-Q&
O
3 eq N M O , OsO, , aq dioxane 2 eq aq N d O , , 60"C, 18 h
w
BnO B n 0
w Ph
*
(TMShNH , inicmwaves , LiClO, F
+
C6H,,0TMS
-83%
rnicmwaves , clay, H 2 0 Bandrar. B.P.; Kasture, S.P. Monat. C h m . , 2001, 132, 1101.
InBr3, aq MtCN
BnOO -Tr
heat. 2.5 h
*
P BnO
O
H
90% yadav. J.S.;Reddy, B.V.S.; Srinivas, R.; Maiti, A. J. Chern. Rex (S), 2001, 528. BiC13 , MeOII, rt , 2 inin P hCI I2OTMS * PhCHzOH 97% Firouzahadi, H.; &&iminad_noor-Baltork. I.; Kolagar, S. Synth. Cornrnun.,2001, 31, 905. PhCH20H ;-
Ac20 , microwaves, 8 min
* PhCHzOAc Kasture, S.P.; Kamhle, V.T. Synth. Conintun. 2001, 31, 2255.
80%
TBDMSCl,DCM,rl chiral quinidine hase
OH Isohe, T.; Fukuda, K.; Araki, Y.;
SO% ( 39% ee) OTBDMS
Clwnz. Contnzun., 2001, 243.
Section 45A
PhCHZOTHP
Protection of Alcohols
Sc(OTf), , MLCNIMLOH
.
79
*
PhCH2OH
84%
also with ROMOM It Watahiki, T.; Kohayashi, Y.; Hirano, H.; Suzuki, T. Synth. Coniinun., 2001, 31, 2305.
;.T-
HC02CI-IPh2 , E4SiH
-0THP Ph
OCHPh2 * PhTMSOTf , silica gelh4eCN 90% 0°C. 1 h Suzuki, T.; Kohayashi, K.; Noda, K.; Orivama. T. Synth. Continun. 2001, 31, 2761.
In
P hCI IZOTHP
,I2 , EtOAc
, reflux, 1.5 h
* PhCHlOAc
also with RMOM Ranu. B.C.; Hajara, A. J. Chein. Snc., Perkin Truns. 1, 2001, 355. Ranu. B.C.; €Iajra, A. J. Chern. Soc., Perkin Truns. 1, 2001, 2262.
80%
Ph,SiH, Korr , 18-crown-6 DCM ,rt
87%
OSiPh3
T.; IICnique, J.; Samuel. E. Chent. Connnun., 2001, 1408.
orr I
PhN=C(Ph)O'IBDPA ,THF
PhA C 0 , E t Misaki, T.; Kurihara, M.;
P hCr 1 , o n r P
OTBDPS
I
*
99%
rt , 3 0 m i n Ph4 0 2 m Clienz. Continun., 2001, 2478.
NH4+ C Q C r , Montmorillonite K10 microwaves, 20 sec
*
PhCHO
94%
Heravi. M.M.; Hekrnatshoar, R.; Beheshtiha, Y.S.; Chassemzadeh, M. Monut. choni.,2001, 132, 651.
orr &C02Et
cJNQ OPMP
, 1.1%Me3SiOTf
DCM, r t , 0°C
Nakano, M.; Kikuchi, W.; Matsuo, J.-i.;
P hCH,OA c
&&C02Et Cheni. Lett., 2001, 424.
10% P( 2,4, 6-trimethoxyphenyl)3
MeOH,5OoC,3 h Yoshimoto, K.; Kawahata, 11.; Nakamichi, N.; JTavashi.
--
QpMp
t
PhCH20H
Chern. Zxrr., 2001, 934.
91%
90%
80
Coinpendiuin of Organic Synthetic Methods, Vol 11
-
1.2 eq BnOMs, 10% LiB(C6F5), LiOTf , 1.6 eq MgO ,it, 1 d
a 0 1 4
cyclohexane-DCM
Section 45A
c1M
O
.
Oxone, MeCN ,reflux, 5 h
.
*
n
97%
Nakano, M.; Matsuo, J.-i.; Mukaiyania, T. Chcm. Lett., 2000, 1352. P hCIIzOSiMq
B
99%
PhCH20H
/\mini, M.K.; Farshidipoor, S. Bull. Cliein. Snc. Jpn., 2000, 73, 2775.
; -
r 2% Sc(0Tfi
Ph
EtCN.. rt .. 30in Suzuki, T.; Wntahiki, T.; Orivama. T. Tm-uliedron Lett., 2000, 41,8903.
88%
ph
EDC, B oBO DMAP, H DCMt-
L
o
C::
Clark, M.A.;
;.T-
1
1
-
o
0
90%
. .
y
B
n
-
96%
€I2,10% Pd / C , EtOAc Tetruhedron L.ett., 2000, 41, 9523. 40% DIIP , SM ~lq Nd3S04
93%
toluene, 30"C, 50 inin
I-Iayakawa, S.;IIirasaka, Y.; Saitoh, M. Tetvuhedron Lett., 2000, 41, 9843.
Mn(0Ach - DDQ
O~MB
n
75%
CHzCl2, rt , 8.Sh
OH
n
Sharma. G.V.M.: Lavanya, B.; Mahalingam, A.K.; Krishna, P.R. Tetrulz~rirnnLett., 2000, 41. 10323.
Section 45A
Protection of Alcohols
81
Iwasaki, F.; Muki, T.; Onomura, 0.;Nakashima, W.; Matsumura. J. Org. Cheni., 2000, 65, 996.
Y,
DMSO, 80°C , 3 6 h Ph-o?-sDMs
* Ph-OH
,P c NMe MeNMeN \
CN23
O3
90%
Yu, 2.; Verkade. J.G. J. 01-g. CIieni., 2000, 65, 2065.
BnOH , BiBq ,CCl,
7
77%
t
OH rt,9Gh OBn Bover.B.; Keramane, E.-M.; Koque, J.-P.; Pavia, A.A. Tetmkedron Lett., 2000, 41, 2891. CKl, , TIIF, cc1,
PhO -H
It
Ph
*
-
O
Y
s
90% Baati, K.;Valleix, A.; Mioskowski. C.; B u m a , D.K.; Falck. J.R. Org. Lett., 2000, 2, 485. Ac20 , Nation-II , rt , 3 h
Kumareswaran, R.; Pachamuthu, K.; Vankar. Y.D, Synlett, 2000, 1652. CSI-I, 10 --
1. t-BuLi , pentane , -7X"C
2. H30'
4
It
*
99%
CSHll-OH
92%
W.F.; England, M.D.; Mealy, M.J.; Thogsomkleeh, C.; Teng, L. Org. &It., 2000, 2, 489. V.
1. BU3SnII, AIBN , PhH 0.0SM d O S i P h 2 S i M e 3
2. MeLi
Studel.;Bossart, M.; Vasella, T. Org. Lett., 2000, 2 , 985.
_.
82
Section 45A
Compendium of Organic Synthetic Methods, VoI 11
Ph
OBn
3% Sc(NTf,), , anisole lOO"C, 2.5 h
-
-OH
--
Ph
92%
Ishihara, K.; Hiraiwa, Y.; Yamamoto. H,Synlett, 20'00, 80. M t O H , 30°C, 19 h H
+,
ph-oH
93%
0
Cl(Bu)2Sn( ;Sn(Bu)zCl 0
H Orita, A.; Sakamoto, K.; Hamada, Y.; O t e r a . S y n k t t , 2000, 140.
PhO
w
Et2NH , Pd(OAc),, TPFTS
+ PhOII (+ allyldietbylamine) sec-( 2,6di-O-methyl)- f3-cyclodexfrin quant
Widehem, R.; Lacroix, T.; Bricout, H.; M o n f l i e r . S y n l e t t , 2000, 722. 3 eq Mg , 3 eq Me,SiCl
OSiMe3 DMF, rt p+ . . Nlshltuchl.;E t a , Y.; Watanahe, M.; Ishino, Y.; Ohno, T.; Maekawa, H. Synlett, 2000, 1025. P
,
i OH
h
99%
I
92% (100% ee)
Yadav. J.S.; Reddy, P.T.; Hashim, S.K. Synlett, 2000, 1049. 20% TiCl4, X M , A ~ 2 0
I'h -onw ;-
I
..
O"C+ r t , 6 h
,
P hCI I,OH 83%J -
OAc * PhM
78% Ramachandar, T.; Reddy, M.V.; Takhi, M. J . Org. Chem., 2000, 65, 4729. dihydmpyran , cat I,, DCM , 3 0 min
t
Ph a 2 - O T H P
MeOH, 12, heat, 3 h Kumar. 1I.M.S.; Reddy, B.V.S.; Reddy, E.J.; Yadav, J.S. Che171. Lett., 2000, 857.
90%
-
Section 45A
Protection of Alcohols
OPMB
83
CBr4, MtOI-I, reflux , 6 h Ph-OH
Ph
Yadav. J.L;Reddy, B.V.S. Chem. Lett., 2000, 566.
OH
-
0.5 DMAP , rt
p-Tol-Cl120CPh,, MS 4A
-0"
97%
5 eq pyrmlidine , THF , BuLi
rt, 16h h i m , X.; Costa, A.M.; Faja, M.; Pine&, 0.;
Ph
87%
DPQ , DCM ,i t , 2 0 inin
Cqt-Bu Org. L ~ t t . 2000, , 2, 2809.
* Ph
Sharma. G.V.M_; Mahalingam, A.K.; Prasad, T.R. Synlett, 2000, 1479.
96%
Bahwa. J.S.; Vivelo, .I.; Slade, .I.; RepiE, 0.;Blacklock, T. Tetruhedron Lett., 2000, 41, 6021. 3 eqBiCl,, 2,4,6-~llidine
C,% -OH
QO
t
c7111S
,6O"C , add over6 h
Barks, J.M.; Gilhert, B.C.; &sons.
-0 88%
U ;Upeandran, B. Tetruherlron Lett., 2000, 41, 6249.
TIPSCl ,imidazole ,micmwavas PhCHzOII t PhCH2OTIPS K h,J .l J f-i ~ t z h a d&; . Alandmi, R.F.; Zekxi, N. Tctrulzedmn, 2000, 56, 7503. 1
C,,,H,,OSEM
10 eq MgBr2/ether/MeN02
-
~loHzloH
Vakalopoulos, A.; Hoffinann. FI .M.R. Org. Lxtt., 2000, 2, 1447. Zr - sulfophenyl phosphonate
* MqCCHGAc AczO, D C M , rt , 15 h . . Cunnl.;Epifano, F.; Marcotullio, M.C.; Rosati, 0.;Rossi, M. Synth. Conzl,lltn., 2000, 30, 1319. MqCCHzOI-I
96%
99%
74%
Compendium of Organic Synthetic Methods, Vol 11
84
Section 45 A
--
92% Yu, W.; Su, M.; Gao, X.; Yang, Z.; .lin.Z. Tetrultedmn Lett., 2000, 41, 4015. DHP, DCM ,Z C l , O -H
OTHP
*
96% MLOH, Z r C l 4 Rezai, N.; Meyhodi. F A . ; &l&iJL Synth. Coniniun., 2000, 30, 1799.
air, Co or Mn salts PhCN,OS i Me, c PhCH,OH )I,J . sheml.;Kalantari, P. Synth. Commun., 2000, 30, 1857. AcOII , La Y-zeolite
PhCH,OI-I
Narender, N.; Srinivnsu, P.; OTH P
I
A
c
94%
80%
PhCXI2OAc
99% 116"C, 8 h ' ' I ; Raghavan, K.V. Synth. Conmzun., 2000, 30, 1887. 01.1
CuCl2.2 If20 ,MtOH z
I ) ,
85%
Ph rt,lh Ph Davis, K.J.; Bhalerao, U.T.; &>. B.V, Synth. Commun., 2000, 30, 2301. ~
~~
Pansare. S.V.; Malusare, M.G.; Rai, A.N. Synth. Commun., 2000, 30, 2587. NaCNBH3 ,MeCN
TMSCl Rao, G.V.; Reddy, D.S.; Mohan, G.11.; w a r . D.S . Synth. Commun., 2000, 30, 3565. PhC€I,OII 89%
-
DIIP, LiBr , DCM
*
LiBr , MeOH ,heat Reddy, M.A.; Reddy, L.R.; Bhanumathi, N.; Rao. K.R. Synth. Commun., 2000, 30, 4323.
Section 45A
Protection of Alcohols
85
C~C13.7H20 , M d I i
PhCH20TIIP Reddy, G.S.; Neelakantan, P.;
* PhCH,OH 30 min D.S. Syntli. Coninum., 2000,30,4107.
90%
PH ZdKPO,), , aq acetone 6O"C, 7 h
Me02C Me02d 79% Curini. M .; Epifano, F.; Marcotullio, M.C.; Rosati, 0.;Rossi, M.; Tsadjout, A. Syntli. Comiirrin., 2000, 30, 3 181. DHP ,cat I,, miaowaves , 7 min
PhCH,OII
91% -.
PhCH,OTIIP
D 4
84% M d H , cat I , , microwaves, 10 inin Deka, N.;Sarma. J.C, Synth. Commun., 2000, 30, 4435.
MrCN , Nd , Me3SiC1
*
2h
Kdmdl.; . . Laxinan, E.; Rao, N.V. Tetrahedron
&ti., 1999,
+OH 98%
40,371.
OSiMqt-Bu t-BuMqSiO
0.1 Nal
t;" u M q S
i
0.1 M MeCN 0.2 TMSCI/H,O Gricco. P.A.; Markworth, C.J. Tetruhcdron Lett., 1999, 40,665.
O
d
o
H
/ 86%
CBr, , MeOH, reflux , 3 h -0mp Ph * PhO -H Lee. A S - Y . ; Su, F.-Y.; Liao, Y.-C. Tetruherlron Lett., 1999, 40, 1323.
91%
Zn@F4h, H 2 0 12 h A. Tetruhedron LL'tt., 1999, 40,1985.
87%
Coinpendium of Organic Synthetic Methods, Vol 11
86
OH I
-
AczO ,CHzCIz , 3 0 min
I
A
Section 45A
-
OAc
I I
A
92%
2.5% C ~ ( 0 T f ) z Ph Tetruhcdron Lett., 1999, 40, 261 1.
Ph Saravanan, P.; &&lJL,K
3% C A N , 70°C ,MeCN CdJI 1- 0 n I P
*
pH 8 borate buffer
OH
C5H11
94% Markti. I.E.; Ates, A.; Augustyns, B.; Gautier, A.; Quesnel, Y.;Turet, L.; Wiaux, M. Tetruiicrirnn LtK, 1999, 40, 5613. e- , PdClz-bipy , DMF, B u P B F ~
PhOCI I ?CH=CII2
*
PhOH
75%
Franco, D.; Panyella, D.; Rocamora, M.; Gomez, M.; Clinet, J.C.; Trtrultedron Lr.tt., 1999, 40, 5688.
* ’\
CeC13*7Hfl,M&N
NaI , rxflux , 6 h
Thomas, R.M.; Reddy, G.S.;
’
BzCl , TMEDA , MS 4A
Ph CHzClz ,-78°C , 2 0 min Sano, T.; Ohashi, K.; Orivaina. T. Synflmis, 1999, 1141
-
>
cat B(C&),
I’h -OH
/J
97%
C
O
\ /
O
H 94%
J . Org. Chein., 1999, 64, 4211. , Ph3SiH , toluene
rt,20h Blackwell, J.M.; Foster, K.L.; Beck, V.H.; PhOAc
-
Ph
electro-generated Ni , AcONa* N D M F , 18 h , r t
YdbUhdld.; , . ... Kasano, A,;
90%
Tetruherlron Lxtt., 1999, 40, 7293.
* Ph
93% W E, J . Org. Chem., 1999, 64, 4887.
PhStI , S % KzCO,, NMP
PhOH reflux, 15 min ; Nayak, M.K.; Shanna, L. J. Org. Chcin., 1999 64, 8027. /
96%
Section 45A
Protection of Alcohols
4
Ph
V$l,
~
~
~
~
a7
,
Ph +OMPM , 4 80% h
*
g
Mahalingam, A.K. J. Org. Chcm., 1999, 64, 8943. CH,=CHOAc, THF , 1 7 h
-H PhO
Ph
B nN=P( NMe&
Ilankulnaran, P.;
99%
w.J.G. J. Org. Cheni.,1999, 64, 9063. Oxone, 58%
‘y-l
MLOH
*
B nO-(CI12k-OTBDMS
3h Sdl. . . G.; Syamala, M.; Yadav, J.S. Org. Lm.,1999, I , 1701.
,’
P hCH,OTI IP
K- 10 Montrnorilbiiite clay
MLOH,rt,Ih Tankguchi, T.; Kadota, K.; El Azah, AS.;
OAc
90%
BnWCH2)r-OH
*
PhCH2OH
91%
Synletf, 1999, 1200.
AcOII ,at FeCl3 , 1 h
* Ph o -*c
O H -hP
99% V.M.; Mahalingam, A.K.; Nagarajan, M.; Ilangovan, A.; Radhakrishna, P.
Synlett, 1999, 1200.
&mfy.
CJ,; Pitts, M.R. Synleft, 1999, 1575
P hCH20H Chauhan, K.K.; o-Ac Ph
O.l%In(OTfh, MeCN ,rt
w PhCH20Ac A%?O Love, I.; Waite, D. Synlett, Z999, 1743.
97%
u;
i-PIOII, =flux, 12 h 10% Yb(OTQ3
Sharina. G.V.M.; Ilangovan, A. Synlett, Z999, 1963.
-
H PhO 95%
88
Compendium of Organic Synthetic Methods, Vol 11
Section 45A
90% hv ,MeOH 85% Brook. M A; Balduni, S.; Mohamed, M.; Gottardo, C. T&-uhedron,1999, 55, 10027. Montmorillonite K10, MeOH CH€Il 7 4 T H P
50°C J.i. T.-S.; Zhang, Z.-€l.; Jin, T . 3 . Synth. Continun. 1999, 2Y, 181. cil t
C8H174H
(y0m;5
a - Z O3 ~ PMe)l .2( O3FC6H4S03H)a .x DCM , TMSZNII ,rt
- .0. O ”
*
; Epifano, F.; Marcotullio, M.C.; Rosati, 0.;Costantino, U. Synth. Conintun., 1999, 2Y, 54 1.
DHP , H2S04 , S i 0 2 , 1 inin PhCH2OI I
+
P hCH2OTHP
4
90%
H2SO4, S i O z , MtOIf , reflux , 15 min
92%
--w9
.Huiw-MX; Ajami, D.; Ghassemzadeh, M. Synth. Coininun., Z999, 29, 1013. 1
.
DIfP , SnC12*2H 2 0
*
Davis, K.J.; Bhalerao, U.T.; B;w. B.V. Syntfi. Coniniun. 1999, 2Y, 1679. TiCI, , EtOAc, 0.85 h PhCH20TMS + €ranpoor. N.; Zeynizadeh, B. Synth. Coniniun., 1999, 29, 2123.
PhCI120Ac
..
89%
PhBF?K, 5% Pd(0Ac)z , DME
* Ph-Ph 99% 60°C. 1 h 4dlltha.; ‘. ,’ Reddy, B.V.S.; Srividya, R.; Yadav, J.S. Synth. Comniun., 1999, 29, 2311. Ph21+BF;
PhCH2 OT HP
Clayan , N114N03 , 3 min
w PhCHzOH miaowaves Me . h .. hldm.;Sumitra, G.; Raddy, G.S.; Ganesh, Y.S.S.;Yadav, J.S. Synlh. Conimim., 1999, 2Y, 2807.
90%
MeOIi, DCM , LBF, C& ,7-OC:Phh2 Ar =p-nlethoxyphenyl
McCN
CJl174H
Chen.;Zheng, Y . ;Zhou, X. Synth. Conimun., 1999, 29, 3421.
94%
Section 45A
Protection of Alcohols
89
-
MOM-Br , NaOMe , DMF
rt , 3 0 m i n
;-
B
r
~
O
\ /
also with ArOSiK3 Noda, K.; Sugawara, S. Synth. Coilitnun., 1999, 29, 2217.
M
O 85%
93% Kajiro. 11.; Mitamura, S.; Mori, A.; fIivama. T. Bull. Chern. Soc. Jpn., 1999, 72, 1553. Ph-OTM S
a t PdCI,(PhCNk, 3 inin
Ph-OH
(also with Montinorillonite K10 , 1min) - quant Mojtahedi, M.M.; &,&-MJL ; Heravi, M.M.; Bolourtchian, M. Monnt. Chcvii., 1999, 1-30, 1175.
qumt
M
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 4 PREPARATION OF ALDEHYDES
SECTION 46: ALDEHYDES FROM ALKYNES
-
C6HI3
2% RuCpCl(dppm) , H 2 0 , 12 h
Suzuki, T.; Tokunaga, M.;
P h =
* C6H13CH2CHO
93%
, i-PlOH, sealed I u ~ 100°C ' Org. Lett., 2001, 3, 735.
1. 5% [ R u ( T ~ ' - C ~ H ~ X P P ~, H2O ~)C~] i-PrOH ,90"C , 2 d * Ph-CHO 2. "1C ~ ~ H 2 ~ S O ~ - N i i + 3. aq. C16H38NMq+Br71%
i-
,( i
Ph
Alvarez, P.; Bassetti. M .: Guneno. ' J .; Mancini, G. Tetrahedron Lett.,2001, 42, 8467.
17%
SECTION 47: ALDEHYDES FROM ACID DERIVATIVES
Ph
Ll
cat InCI3 , Bu,SnII ,toluene
0.2 PPh3 , -30°C , 2 h
Phl
H
97%
Inoue, K.; Yasuda, M.; Shihata, I.; Baha. A. Tetruhedron Lett., 2000, 41, 113.
8,
1. AlH, * 2. PCC Bu Bu Cha.;Kim, J.M.; Chun, J.H.; Kwon, 0.0.;Kwon, S.Y.; Han, S.W. Org. Prep. Procced Int, 1999, 31, 204.
h PhCHO 3. P c c Lee, D.Y.; Kim, J.M. Org. Prep. Proceed. Int., 1999, 31, 694.
PhCO,H
C2hrd.L;
1. NaBIl4 2. M%S04
95%
82%
Section 48
Aldehydes from Alcohols
91
SECTION 48: ALDEHYDES FROM ALCOHOLS AND THIOLS P hC€I,OH
Pd(II)-hydrohlcite , toluene, air
t PhCH0 98% 0.2Py,65"C,3 h Kakiuchi, N.; Maeda, Y.; Nishimura, T.; J. Org. Chem., 2001, 66, 6620.
PhCH20H
DMSO, T H F ,-30°C
B-
PhCHO
91%
4 N-("
N99% Chertt. LEN., 2001, 846.
D.;Kitagwa, H.
zeolite OMS-2, air PhCH20H Son, Y.-C.; Makwana, V.D.; Howell, A.R.; Angew. Chcnt. Int. Ed., 2001, 40, 4280.
+
PhCHO
(NH4)2Cr~07,HIO3, wet Si02
PhCHO 30 min Shirini, F.; Zolfigol, M.A.; Azadhar, M.R. Russ. J. Org. Chem., 2001, 37, 1600. P hCH20H
P hCH20H
95%
calcium hypochlorite , moist alumina
*
PhCHO
85%
87%
98%
m i m w a v e s , 1 min Mojtahedi, M.M.; Saidi. M.R,; Boloui-tchian, M.; Shirzi, J.S. Monot. Chem., 2001, 132, 655.
Compendium of Organic Synthetic Methods, Vol 11
94
Section 48
(NH,h%O, , AgN03, hexane
PhCH2OH
PhCHO 99% Montmorinonite ,60"C, 25 h Hlrdno.; Kojima, K.; Yakahe, S.; Morimoto, T. J. Chenr. Res. (S), 2001, 274. (NH& Cr207 ,XI., ,0.05 h
* PhCHO wet SiO, , solvent fm .. . Shlrlnl.; ali Zolfigol, M.; Pourhahih, A. J. Chem. Res. (S), 200Z, 476. PhCHZOH
Br*(collidiieh PF, , DCM , 2.5 h
PhCH,OH
~ o u s s e a u .G .; Rohin, S. Tetruhedron Lett., 2000, 41, 8881. cat Pd(0Ach , toluene , 8 0 T perfluomdealin ,MS 3 A . 10 h
c I I H*,CH,OH
4
*
92%
75%
PhCHO
c 11 H
* P O
76%
fluoroalkyl a e t a l pyiridine ligand Nishirnura, T.; Maeda, Y.; Kakiuchi, N.; IJemura. S. J. Clietn. Soc.,Perkin Truns. 1, 2000, 4301. PhCI 1 2 0 1 ~
;-
. ,
/
Ph-CHO
Cs2C03 , 100°C. toluene Tetruhedron Lett., 2000, 41, 7507.
Lee, M.; PhCI1,OH
5% [RuCb(p-cymene)z , O2
1.5
Ph(Cl)S=Nt-Bu. 2
DBU
+ PhCHO DCM ,-78"C, 30 inin Matsuo, J.-i.; Yanagisawa, M. Chem. Lett., 2000, 1072.
catBu4NBr,II2O2,DCM.1 d
* C,H,,CHO a t [Ru,O(OAC),~(M~OH)~] OAc Wynne, J.11.; Lloyd, C.T.; Witsil, D.R.; Mushrush, G.W.; &ikk. W.M. Org. Prep. Proceed. Int., 2000, 32, 588. C,H ISCH*OH
Barrero.; Alvarez-Manzaneda,
91%
-
98%
67%
E.J.; Chahhoun, R. Tetruhedron Lett., 2000, 41, 1959.
Section 48
Aldehydes from Alcohols
TEMPO, Oxone , rt
PhCZlO
PhCHzOH
DCM,BulNBr
Bolm.;Magnus, A S . ; Hildehrand,
95
90%
J. Org. Lett., 2000, 2, 1173.
mCHO
N i B Q , AcOH , 7 h PhO *H
* Ph 46% reflux, H$I B a n k B.K.; Ghatak, A.; Ventraman, M.S.; Decker. I.F. Synth. Commun., 2000, 30, 2701 his(1 -heiizy1-3,5,7-triaza-lazoniatricyclo[3.3 .I. i3J1 d m n e
P hCZ12OI-I
t
peroxydisulfate , MLCN
PhCIIO
98%
Minehu W.; Guichun, Z.; Zuxing, C. Synfh. Commun., 2000, 30, 3127. BnPPh3+Ci03*HCI,MeCN
PhCH2OH
*
PhCHo 85% reflux, 25 min ; Backnejad, H. Synth. Continun., 2000, 30, 3855. C Q ,70%TBHP
* PhCHO 87% microwaves, 10 inin Sineh.;Shanna, M.; Chhihher, M.; Kaur, J.; Kad, G.L. Synth. Commun., 2000, 30, 3941. PhCH2OH
pol y [vinyl@yridiniumfluoroc hmmate)]
*
PhCH,OH
PhCHO
95 %
acH
cyclohexane , rt , 15 inin Srinivasan, R.; Balasuhramanian, K. Synth. Coiiwiun., 2000, 30, 4397. OH
2% prfluornalkyl suhstituted hipyrkline , CuBr-SMe,
96% 3.5%'OTEMPO,90°C. 0, CaF18PhCI Br Betzerneier, B.; Cavazzini, M.; Quici, S.; Tetruhedron Lett., 2000, 41, 4343. P hCI 12OH
ZINO3,10% Yh(OTf), , DCM
.c PhCHO 91% x f l u x , 30 min Braddock, D.C.; McKinnell, R.M.; Waller, F.J. Synfett, 1999, 1489. W e t t . m;
NaNOz-Acg, 25°C C,HFH,OH
-
C3HFHO
60% B . P i Sadavarte, V.S.; IJppalla, L.S. J. Chem. Sor., Perkin Truns. 1, 2000, 3559. c: 1 inin
Compndium of Organic Synthetic Methods, Vol 11
96
.
; -
,
78%
microwaves, 3 min Khoee, S . Synlett, 2000, 740.
.
Th(III)-pol ypyridine complex PhCHzOH Knlle.; Frinzl, €1. Mnnat. Chem., 2000, 131, 1321. Ph
Section 48
Ru-CO-Al hydwtalcite ,Oz
OH
toluene, 6O"C, 40 min
PhCHO
c
-
mCH
Ph
89%
Matsushita, T.; Ebitani, K.; Kaneda. K. Chem. Conintun., 1999, 265. PhCHzOH
zeolitt: €ESM-S-supporttx Fe(JI1j nitrate
w PhCHO 99% micmwaves , 10 sec Ikravi. M.M,;Ajami, D.; Aghapoor, K.; Ghassemzadeh, M. Chem. Cornrnun., 1999, 833
silica-supported TEMPO, DCM
PhCH,OH
aq KBr , aq NaOCl, NaHC03 (pH9.1) Balm.; Fey, T. Chern. Cornrnun., 1999, 1795.
75%
PhCHO
Lr
KMn04/alunina , no solvent
* PhCIIO 30 z c €1a"iinour. A.R.; Mallakpour, S.E.; Imanzadeh, G. Cheni.Lett., 1999, 99.
94%
PhCH,OH
dCH q=o
S i O z ,CHzClz
-
ACID4
Kernag, C.A.; &hhitt.
0
89%
J.M. ; McGrath, D.V. Tetrahedron Lett., 1999,40, 1635.
CdI I~CH~CHIOH
1 % Os04 , 1.5% CuCl ,O2( 1 a h j s%I
P Y , MS 4 A , toluene, IOOT
c
C&13CH2CIIO
32% hetteryiekls with benzylic alcohols Coleman, K.; C o p p , M.; Thomas. C.; Tetruhedron LEtt.. 1999, 40, 3723.
Section 48
97
Aldehydes from Alcohols
PhCHzOH
CuC1-PhedPhH, 2
2
KZCO,
* PhCI-I0 86% ,IEflux , 2h Mark6 I.E.; Giles, P.R.; Tsukazaki, M.; ChellC-Regnaut, I.; Gautier, A.; Brown, S.M.; Urch, C.J. J. Org. Chain., 1999, 64,2433. 0 2
5% Pd()Ac), , Py , MS 3A
* PhCHO qumt toluene, 8 0 T , O2 Nishilnura, T.; Onoue, T.; Ohe, K.; Ilemura. S. J. Org. Chent., 1999, 64, 6750. PhCH, OH
c61113
or-Bw
BiCl, , CHC13 * PhCHO reflux, 10 min ; Aliyan, H. Syntlz. Conintun., 1999, 2Y, 2731.
90%
I2 , MLCN ,reflux PhCI I=N-OH Ir PhCIIO v. J.S, Sasmal, P.K.; Chand, P.K. Synth. Commun.,1999, 2Y, 3667.
96%
SECTION 6OA: PROTECTION OF ALDEHYDES K2Fe04 , Montmorillonite K10 Ir
E M , reflux , 10 inin ; Ilahihzadeh, S.; Ghassemzadeh, M.
bravi. . , .. . s Monat. Chom., 2001, 1.32, 985.
PKHO
95%
Compendium of Organic Synthetic Methods, Vol 11
108
Section 60A
N-Me-piperidiniun Q03Cp, AlZO,
* PhCHO dioxane ,reflux , 3 0 min .M.; Mohanazadeh, F.; Sarahi, S.; Ghassemzadeh, M. Monot. Chcm., 2001, 132, 1229. PhCH=NOH
IIS(CH2hSH. CdIz, 75 S
~ C
PhCHO
.-cI>
*
microwaves
85%
Sandhu, J.S. J. Chein. Res. (S), 2001, 313.
Laskar, D.D.; ;-
O.l%Bi(OTf),=x H z O , MeCN
PhCHO
3qAriO
Carrigan, M.D.; Eash, K.J.; Oswald, M.C.;
‘
4
0
A OAcc
91%
Tetruhedron Lett., 200Z, 42, 8133.
HSCIIzCHzSII,Iz, A 1 2 0 3
P hC1I 0 Deka, N.;
92%
I
10 min Cheni. L.ett.. 2001, 794. cat N z 0 5 , H 2 0 2 ,NH.,I3r, 5 h
* CllH23CH0 DCM/HzO, 1.75 h Mondal, E.; Bose, G.; Sahu, P.R.; Cheni. Lett., 2 U U 1 , 1158. C11 H,,CH(SEt)2
80%
HSCH-CIIzOH, 2101nin , DCE P hCI I 0 a t r ~ ( d P P ~ ) ( P - O H )(BF,), l,
* ]:(--hp
90%
MgSO,, HzO Battaglia, L.; Pinna, F.; Strukul, G. Ccm. J. Chcrn., 2001, 7Y, 621. 3 eq CIC12,4 q LiI, aq EtOAc Ph
75°C. 12 h
T .,dl . ck.;Baima, D.K.; Baati, P.; P hCIIO
92% Mioskowski, C. Angew. Chmt. Int. Ed., 2001, 40, 1281.
HS(CII,),SH , cat LiOTf, 0.1 h solvent f ~ e
*
Ph ‘SJ
rllDUZdhrldl.; .. . , Eslami, S . ; Karimi, B. Bull. Chein. Soc. Jpn., 2001, 74, 2401.
99%
109
Protection of Aldehydes
Section 60A
H S C H ~ C I - ~ ~ C H Z0.1 S HI,2 rt , 10min
P h q o OMe m
f.'irouzahadi. K; Jrannoor. N.; Hnzarkhani, €1. J. Org. Cli~nz.,2001, 66, 7527.
1.2ethanedithbl k1C13, MeOH 15 iiiin 92% Muthusamy. S.; Bahu, S.A.; Gunanathan, C. Tetruherlron Lxtt., 2001, 42, 359.
PhCIIO
HSCIIzCH2SH. LiBF, MtCN ,rt, 1 h
Yadav. J.S.; Reddy, B.V.S.; Pandey, S.K. Synlett, 2001, 238.
cetylMe3N-Br3 , 5 rnin.r CHz(32
M
e
O
0-
C
H
HOC€12CH2011,ZrPS03H ~
~
90%
~
CIIZC1,, reflux , 1 h
. . Cunnl.; Epifano. F Marcotullio, M.C.; Rosati, 0. Synlett,, 2 0 0 1 , 1182. Ph+OMe 0 Me Ono, F.; Negoro, R.;
PhSH ,2076 LiBr toluenc , 25°C
*
Ph+OMe
90% SPh
Synlett, 2001, 1581.
claI] K@)W12040*31120
acetone, reflux , 1 h *
97%
U . ',' Tangestaninejad, .M S.; Mohamnmadpoor-Baltork, .H. I.; Mirkhani, ; V.; Yadollahi, B. Tetruherldon Lrtt., 2001. 42, 6771.
O
93%
Mondal, E.; Bose, G.; Khan. A.T. Synlett, 2001, 785.
CI-I0
O
\ /
Coinpendium of Organic Synthetic Methods, Vol 11
110
Section 6QA
€ISCH2CH2CH2SH,0.75 h ,r t
c1
Ph4O"^ OMe
YAYu"CIICl., 0
v; . * I-Iazarkhani, H. Synlerr, 2001, 1641. '1.
AczO , 10%LiBF, ,40"C
Ph C I O
PhCH(OAc),
t
20 h Sumida, N.; Nishioka, K.; Sato. T. Synlett, 2001, 1921.
95%
Samajdar, S.; Basu, M.K.; Becker, F.F.; Banik. B .K. Tetrahedron Lett., 2001, 42, 4425.
PhCHO
O.l%Bi(OTf)3*xH 2 0 , MeCN
* Ph99%
Tetruhedron Lett., 2001, 42, 8329.
*
Ph4:] 84%
. . Balllnl.; Bosica, G.; J&ggLL Mazzacani, A,; Righi, P.; Sartori, G. Synthesis, 2001, 1826.
ph.r > 4
' 7 .
cdi ,1-
. .
cr 10
N.;K a r h i , B. Synlett, 1999, 319. (EtO),CH ,ZiClq, neat
~
N,; Karimi, B. Synlert, 1999, 321. rIscIi,cIr,sH,
Anand, K.V.; Saravanan, P.;
neat , 2
11
97%
+OEt
It
qumt
S
OEt
cu(o~~--sio,
m.V.K, Sywlett, Z9Y9, 415.
c & 1 3 4 ; 3
93%
Section 60A
Compendium of Organic Synthetic Methods, Vol 1 1
114
PhCHO
1 . 3 eq (EtOhCH, E O H , rt DCM,NBS 2.10% aq NaOH
95%
OEt
. . Kanml.; Seradj, H.; Ehrahimian, G.-R. Synletr, 1999, 1456. (EtO),CH ,cat DDQ, rt t
P hCHO
95%
EtOH , 10 h
. .
OEt
anmi. B.; Ashtiani, A.M. Chenr. k'tt., 1999, 1199.
PhCHO
ethylene glycol ,CdIz , 1.5 min mi an w ave s
=-
ph--(I]
90%
Laskar, D.D.; Pra.iapati. D, ; Sandhu, J.S. Cheni. Len., 1999, 1283.
P hCHO
IISCH2CIi2CHlSH ,HCI, AcCl , MeOH , 2 min
. .
Synth. Coriirnun., 1999, 29, 697.
Clayan , microwaves P h 4 s ESE tt
110 yec
89%
PhCHO
t
Meshrain. H .M.; Reddy, G.S.; Sumitra, G.; Yadav, J.S.Synth. Commun., Z999, 29, 1113. (Et0)sCH , cat WCl6
* PhCH( OEt), neat, rt , 10 min Firouzahadi H . Irarlnoor. N.; Kariini, B. Synth. Commun., 1999, 29, 2255. P hCHO
Ph
NO2
A1-NiCl2-CH20 ,TIIF
Bezhiirun, M.S.; Bez, G.; Barua. N.C. Chcwi. Lett., 1999, 325.
t
98%
Ph-CHO
77%
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 5 PREPARATION OF ALKYLS, METHYLENES AND ARYLS This chapter lists the conversion of functional groups into methyl, ethyl, propyl, etc. as well as inethylene (CHl), phenyl, etc.
ALKYLS, METHYLENES AND ARYLS FROM ALKYNES
SECTION 61:
-
10% Ni(cod)z, 40% PPh3
toluene, it ,0.25 h
&do. S.; Kawasaki, T.; Tsuboya, N.; Yainamoto. Y. J. Org. Chcni., 2001, 66, 796.
Ph
=
Pd(PPh3)4, T H F , 100°C , 12 h Bu
= =
m;
Bu
* P
. I . Radhaluishnan, IJ.; Yakeda, A,; Rubin, J. Org. Chent., 2001, 66, 2885. 1
h
-
Q
X
B
M.;Rubin, M.;
’ U
Ph
“Ph I-hang, Q.; Hunter, J.A.; h o c k .
Bs. . Org. Lrtt., 2001, 3, 2973.
68%
I I
116
Section 61
Cornpeiidiuin of Organic Synthetic Methods, Vol 11
Phi-PPh
? Org. Lett., 2001. 3, 30x3.
1.
Bu
*
5% Pd(OAc)z, 10 h 5% PPh3, NBu3 100°C
'tBr Zhang, H.;
,DMF
=
=S -O2Tol (C3&)Ti(Oi-Prh, -50°C
Bu 2. -S02T0l 3 . H+
Bu
I&
54%
9 f"
SOzTOl
65%
Suzuki, D.; Ilrahe, H.; Sato. F. J . Anz. Cheriz. Soc., 2001, 123, 7925. B
u
e
, PhII,rt
~ r ( c ~ d ) C l ] ~ d p 201nin pe, 84%
Takeuchl.; Tanaka, S.;Nakaya, Y . Tetrulzedron Lett., 2001, 42, 2991. 5% KhCI(PPh,), , 10%AgBFq CHCS ,50"C, 2 h
83 %
Oh.;Sung, H.K.; Jung, S.H.; Lim, Y.M. Tetruhedron Lett., 2001, 42, 5493.
10% [Rh(C0)2Cl],
toluene, 110°C
J.W. Tetruhidron Lxtt., 2001. 42, 5x09.
51%
Section 61
Alkyls from Alkynes
-
117
q~'oqcoz~
C
mt Pd(0Ac)z miaxow aves
Lettner. C..G.; Kiinig, W.A.; Stenzel, W.; Schotten. T. J. Org. Cheni., 1999, 64, 3885.
0
Ph- B(OII), , H 2 0 , rt
Br BudBr, 2 h Bussolari. J.C.; Rehhorn, D.C. Org. I A t . , 199Y, 1, 965.
O
P
h
45%
150
6
Section 70
Coinpendium of Organic Synthetic Methods, Vol 11
Br
Br
C02Me
%08 ' $ C02Me
Shen. W.; Wang, L. J. Org. Cl~cwz.,Z9Y9, 64, 8873.
SiMe,OI-I
PhI, Cat Ph(PPh,)4 * Ag20,l'HF ,6O"C, 36 h
M
e
O
O
\ /
P 80%
h
Hirahayashi, K.; Kuwashuna, J.; Nishihara, Y.; Man.; Hiyama, T. Org. Lett., 1999, 1, 299. 8% Pc/C , air, Zn , overnight
P h-Ph
94%
+ Ph-Ph 50% hydroquinone IIennings, D.D.; Iwarna, T.; pawal. V.H. Org. Lett. 1999, I, 1205.
96%
P h-I
b
HZO/acetone, rt Venkatranian. S.; 1.i. C.-J. Org. Lett. Z999,1, 1133.
Ph-I
2% Pd(OAc), , 2% As(n-Tol)3 C ~ 2 C 0 3,0.4M , 7 5 T , 3 h
P h 3 h , TI-IF, flux cat PdC1APPh3), , 1 h
A
Perez, I.; Sestelo, J.P.; Sarandeses. L.A. Org. Lxtt. Z9Y9, I, 1267. B d n B r , Pd(dha)z, 2 h dppf , Bu4N1, T I I F , 60°C
Piher, M.; Jensen, A X . ; Rottlinder, M.; b c h e l .
Org. Lc?tt., 1999,1, 13223.
94%
Section 70
Alkyls from Halides
15 1
10%Pd(PPh3)4, NMP 80"C, 3 h
80% Et
Rao, M.L.N.; Shimada, S.; 0
W
0
1
Org. Lett. 1999, I , 1271. b
2
, 5 % Pd" , KF
* G neat, A120, ,80"C Kahalka. G.W.; Pagni, R.M.; Hair, C.M. Org. Lett., 1999, 1, 1423. PhI
OBr
P
h
"%
10%Pd(OAc)z, 20% PPh3
PhSi(OMe), , 2 eq TBAF DMF , 8 5 T Mowery, M E . ; DeShong. L O q . Lett., 1999, 1 , 2137. 2
82%
o\
PhB(OI32, K2CO3 , reflux c1
5% Ph(PPh3)4,8 h toluene&IPIEtOH
N
Ph
80%
I,ohse.; Thevenin, P.; Waldvogel, E. Synlett, 1999, 45. 2.5%PdCl(x-GHS), , DMSO
Ph-I
Ph-Ph TBAF, 120"C, 4.5 h A l b m e . D,; Landini, D.; Penso, M.; Petricci, S. Synlett, 1999, 199.
0
82%
PhOTf , Pd2(dhah*dha, D M F
12% c h i d hiaryl bis-phosphine * QPh 3 eq i-Pr2NEt, 90°C. 20 h Tietze. L.F.; Thede, K.; Sannicolh, F. Chcwi. CO/?l/l?I4n.,1999, 181 1.
Me( CH &XCH,Cl Alonso, F.; Radivoy, G.;
NiC12-2 H2O ,Li , 5 % dThh
*
90% (90% ee)
Me(CH&&H,H
dTbli = d,4'-di - t- hut ybiphe ny 1 Tctruheclr-on, 1999, 55, 4441.
55%
152
Compendium of Organic Synthetic Methods, Vol 11
Section 70
BuI , e - , 70"C, T H F , 3 h Pd[F'(o-Tolh]zClz electmgenerated reactive Zn OMe Jurono, N.; Sugita, K.; Takasugi, S.;
.
79% OMe Tetruhedron, 1999, 55, 6097.
GBr
PhB(OH), , dioxanc , 8 h NiCl,(hipy) , Na,P04 70%
LeddtLdter.; , 11, Resouly, S.M. Tetruhedron, IYY9, 55, 11889.
Ma, H-r.; Wang, X.-h.;
59% toluene, 85°C Synth. Conziiiun., 1999, 29, 2477.
MnACOha, DCM hv 88% Gilhcrt, B.C.; Lindsay, C.I.; McGrail, P.T.; J'arsons. Syntlr. Coiiiiiiun., 1999, 29, 271 I. 1. BuLi, THF 2.BF3
\
3. PhBr , PdClz(PPh3h
+ D
P
\
Me Me Lshikura. M.; Agata, I.; Katagiri, N. J. Heterocyclic Chena.. 1999, 36, 873.
h 80%
Section 7 1
SECTION 71:
153
Alkyls fivm Hydrides
ALKYLS, METHYLENES AND ARYLS FROM HYDRIDES
-
-
This section lists examples of the reaction of RH RR' (R,R' = akyl or aryl). For the reaction C=CH C=C-R (R = alkyI or aryl), see Section 209 (Alkenes from Alkenes). For alkylations of ketones and esters, see Section 177 (Ketones from Ketones) and Section 113 (Esters from Esters).
96% (80%ee) Chieffi, A.; Kamikawa, K.; Ahman, J.; Fox, J.M.; Buchwald. S.L. Org. Lett. 2001, 3, 1897.
0 OIIPS
H.M.L.;Ren, P. J. Am.
(65 : Chenz. Soc., 21101, 123, 2070.
35) 80%
10%[Mo(CO),(EtCN),] , 70°C lS% chiral diamine ,NaH, T H F
Ph
CII*(CO2Me)2 , 3 h
Ph
*a 70% (99% ee)
Glorius, F.; Neuhurger, M.; .&&&L Hclv. Chim. Actu, 2001, 84, 3178.
h & W O r , hoton Sponge Me,Si
-20°C
Me3Si
An =p-(MeO)-C,HjIIerrlich, M.; I-Iampel, N.; Org. L m ,2001, 3, 1629.
CHAnz
53%
154
Section 71
Compendium of Organic Synthetic Methods, Vol 11
0 N
*o
1. 1.3eq sec-BuLi, 1.3eq diarnine -78"C, 5 h
I
I
41% (53% ee)
Boc
B oc
Harrison, J.R.;
s &fe3
""UII,
N
2. MqSiCl ; Porter, D.W.; Smith, N.M. Cheni. Commun., 2001, 1202.
1. PhOCOCl , EtMgCl CuBr-DMS ,TIIF
C%Et
2. DDQ , i-PlOAc
&
C0,Et
*
44%
N Wallace. D.J.; Gihh. A.D.; Cottrell, I.F.; Kennedy, D.J.; Brands, K.M.; Dolling, U.H. Syntlwsis, 2001, 1784. cat ReBr(CO)S , t-BuC1* DCE,84"C ,301nin
.
0
t
0
o
t
\ /
+
.. . m; Kakushou, F.; b ,
E
-
B
"
63%
35% 2,Gili-t-Bu)
d a. N,Bull. Chmn. Soc. Jpn., 2000, 73, 2779.
.A%,, N
1% Rhcatalyst with DOSP chiral ligands
Pavies. 1I.M.L.; IIansen, T.; Churchill, M.R. J. Ant. Chem. Soc., 2000, 122, 3063.
COZE t
-0Ac
7
K2C03
1% Pd(PPh,), ,30"C
S% T i i t O X - 1 0 0
ncl
K d.x.y. d ~ LLam, ~ . ; W.W.-L.; Manahe, K. TetruRedron Lett., 2000, 41, 61 15. 1. 3 eq BuLi-MqNCf12C€120Li hexane, -78°C 2 . 4 eq Me1 ,THF , 1 h C1 -78°C -5. 0°C Choppin, S.; Gros, P.; Fort. y. Org. Lett., 2000, 2, 803.
Me
70%
155
Alkyls from Ketones
Section 72
Elliott, (3.1.; Konomlsk . i. J.P.: Olmstead, M.M.
01-6'.
Lctt., 1999, I, 1867.
Sih4e3
LSiMe3 Ph
6 eBr -6" ' Ph
Lenges, C.P.;
88%
5% Rhcatulyst
J . Aim Chern. SOC., 1999, 121, 6616.
,Na , Py,CuC12
ether
Tan.;Zheng, X.; Ma, Z.; Gu, Y. Synth.
SECTION 72:
A
66% (40160 o/p) 123.
ALKYLS, METHYLENES AND ARYLS FROM KETONES
?be conversions R$=O
Ph
Coiiinticn., 1999, 2Y,
-
R-R, RzC€I?, RzCHR', etc. are listed in this section.
T i c 4 , toluene ,reflux
*
/4
Ph
Li, Z.; Sun. W.-H.; Jin, C.; Shuo, C. Synlett, 2001, 1047
Ph
65%
Section 74
Coinpendiuin of Organic Synthetic Methods, Vol 11
156
B(i-Pr)z $1
P h&CO
, ether
4 eq NaHCO3 , overnight -1O"C-. It
65%
Xahalka. G.W,; Yang, K.; Wang, Z. Syntlz. Coninrun., 2001, 31, 511.
L
m S i M e 3
+
67%
HSiMe,Cl , DCM , r , 2 h
Ph Yasuda, M.; Ohishi, Y.; Ito, T.;
SECTION 73
, 5 % 1IlCl3
Ph Teti-uhrclron Lrtt., 2000, 41, 2425.
ALKYIS, METHYLENES AND ARYLS FROM NITRILES [PhMgCi , t-BuOK, TMF 60°C. 1 h]
i
M
t
5 % CI2Ni(PMq)2, 6O"C, 1 h
M l l l e r . T e t r u l t e t l m n k , t t . , 2001, 42, 6991.
Zhu.;Shia, K.-S.; Liu. H.-J, Tetr-uh~~cli-nn L.ztt., 1999, 40,7055.
SECTION 74:
\ ) /O
K
P
91%
80%
ALKYLS, METHYLENES AND ARYLS FROM ALKENES
The following reaction types are included in this section:
A. B. C. D. E. F.
Hydiagenation of Alkenes (and Aryls) Formation of Aryls Alkylations and Arylations of Alkenes Conjugate Reduction of Conjugated Aldehydes, Ketones, Acids, Esters and Nitriles Conjugate Alkylations Cyclopropanations, including halocyclopropanntiotis
h
157
Hydrogenation of Alkenes
Section 74.4
SECTION 74A: HYDROGENATION OF ALKENES (AND ARYLS) Reduction of aryls to dienes are listed in Section 377 (Alkene-Alkene).
ASYMMETRIC HYDROGENATIONS enzyme NAD PH YNAR-I= PhLNo2
-
-k
-
Ph%Noz
(2 3) 31% >98% ee) >97% G% Kawai. Y.: Inaha, Y.; Hayashi, M.; Tokitoh, N.Tetruhedron Lett., 2001, 42, 3367.
phTNo2 Bakers yeast, glucose, 7 h
EtoII , ri20 * p h 7 N T 2 % (17%ee, S ) b w a i . Y,; Inaha, Y.; Tokitoh, N.Tetruliedron Asynzm., 2001, 12, 309.
Filho, E.P.S.; Rodrigues, J.A.R.;
I
Tetruhedron Asymm., 2001, 12, 847.
Am2Me + A CW2Me
Hz ,cat [ R ~ ( C ~ ~ X S - B I N MBF, O)]
Ph
NH Ac
Zhang, F.-Y.; Kwok, W.H.;
DCM, 10 min
,
C02Me Subrez, A.; W m o ,
NHAc
quwt (84% ee) Tetruliedron Asynim., 2001, 12, 2331.
HZ ,DCM ,fl [Rh(codXWP)] BF, Me02
Ph
*
Me02
C02Me
POP = phosphine-phosphite ligand
4. Tetruhedron Asyrnni., 2001, 12, 2501.
99.8%ee
158
Compendium of Organic Synthetic Methods, Vol 11
Section 74A
polymer- suppoiterl BI NAP Ru@INAP) , MLOH
Hz , NEt,
a
ML O Fan.; Deng, G.-J.; Lin, C.-C.;
‘
I
quant (96% ee) Me0 Tetruhedron Asymm., 2001, 12, 1241.
B a k e s yeast 14h
* 12% (>99% ee , s)
KdWdi.; . . Hayashi, M.; Tokitoh, N. Tetruherlron Asynzni., 2001, 12, 3007.
I
I
50 bar H 2 , cat Ir(cod)-chid oxamline
Ph
DCM
Ph
Blankenstein, J.; Pfaltz. A. Angew. Chenz. Int. Ed., 200Z, 40, 4445.
0 *N Ph
[Rh(P-P*)(cod)] BF, ,MeOH 50 bar IIz ,It
P--P* = chiral his phosphine
*ci “t
Tararov, V.I.; Kadyrov, R.; Riermeier, T.H.; Holz, J.; Borner. A. Tetruhedron LEtt., 2000, 41, 2351.
CQMe
=-L
quant (97% ee)
Ph
>99% (up to 50%ee)
[Rh(codh] PF6, DCM, rt phosphine ligand, 1.3 bar H2
COzMe
Reetz.; Mehler, G. Angew.
rt,20h quant (97.6%ee) Chenz. Int. E d , 2000, 3 g 3 3889.
Hydrogenation of Alkenes
Section 74A
159
1% [Rh(cod),]PF6 , 1.1%chird his phosphine
*
3 atinH2, MeOH , rt, 12 h
NHAc
4a2H NIIAc
quant (>99% ee) Tetruhedron LEtt., 1999, 40, 6701.
Li, W.; Zhang, Z.; Xiao, D.;
RR-(EBTHI)-ZrMe2,1700 psi Hz [PhMqNH]' @3QF,]4It, 13-21 h
EBTHI = e~ylenehistetrahydroiiidenyl Troutman, M.V.; Appella, D.H.; COzMe Ph
NHAc
87% (93% ee; >99:1 cis:tmm) J. Am. Chem. Soc., 1999, 1221, 4916.
1% adamantyl-his-P*, MeOH I12,rt,2h
NHAc
Ph
99.9% ee ,R
o. T, Org. Lt~tt.,2001, 3, 373.
*M MLoq NON-ASYMMETRIC HYDROGENATIONS Hz , Pd h h c k ,PhH 4h
-
MeO
MeO
quant
Makl.; Okawa, M.; Matsui, R.; IIirano, T.; Niwa, II. Synlett, 2001, 1590. t-BuNIIZ.BII3 , 10% Pd-C MeOII, sealed vessel
mPh
ph * Ph rt , 4 h Couturier.; Andresen, B.M.; Tucker, J.L.; Dubt, P.; Brenek, S.J.; Negri, J.T. Tetruhcrlron LEtt., 2001, 42, 2763. Ph
Ph&COZH
cat RhCl(PPh3)3, DMSO mimwaves Desai, B.; Danks. T.N. Tetruhedron Lett., 2001, 42, 5063
-
Ph
93%
C4H 95%
-
160
-
Compendium of Organic Synthetic Methods, Vol 11
Ph
Et,SiH, TFA ,-10°C
NHC02Et
Masuno, M.N.;
*
30 min *
Tetruhedron .Lett.. 2001, 42, 8263.
Section 74A
NHCO2Et
Ph
Na2Cr20y2 H 2 0 , DCM * rt . 10 tnin ; Karami, B. Synth. Cornniun., 2001, 31, 3183.
97%
Section 74B
Formation of Aiyls
167
fi
EOZC PhI(0Ac)z , DCM
COZEt
MeHN
&,2h
P
Zhang, P.-F.; &n.
87%
Z.-C. Synth. Conintun., 2001, 31, 1619.
\
Ph
*
COZEt
2S eq %rBPd(PPh3)4,5O"C, -/ , 2 12 eqZiBrz h *&h
/
Ph
Duan, Z.; Nakajima, K.;
.,
/ 59%
Cheni. Comrnun., 2001, 1672.
acetophenone, KOH cat Gruhbs'catalyst , 80°C
00. C.S.; Kim, B.T.; Kim, T.-1.;
. Chent. Contmun., 2001,
,N
Ph
2576.
a t Pd(PPh3)4 , DMF
B u f i C l , 80°C
Tsutsui, 1-1.;
Clrern. Lett., 2001, 526.
1. pipmidine, AczO, 85°C EOAc , toluene , 1 h * 2. 150°C. 3 h
Wei, L -L.; IIsune. R.P.; Sklenicka, H.M.; Gerasyuto, A.I. Anxew. Clteni. Int. Ed., 2001, 40, 1516.
77%
80%
Compendium of Organic Synthetic Methods, Vol 11
168
Section 74B
Ph
I
Ph hv , hexane Ph
Ph
w; Cam, M.; Rodriguez, M.A. Tetmherlron Lctt., 2001, 42, 3575.
82%
S . ; Oh, D.H. J. Heterocyclic Chetn. 2000, 37, 1315.
Cho, C.S.; Oh, B.H.;
Br ,THF . Et
cat NiCl,(PPhs)* Et
Wang, H.; Tsai, F,-Y.;
'
43%
Et Et
TN
Cheni. k t t . , 2000, 1410.
1. B uNI ILi ,T I IF 2. aq IT
*
CN
/
BU
Wang, A.: Zhang, H.; Biehl, E.R. Heterocycles, 2000, 53, 291.
NaNO,, C2H204*2fIzO
CO2Et b
98%
DCM , wet SiO, ,it
H
93%
/N
u '> Kiany-Borazjani, ; M.; Sadeghi, M.M.; Mohairunadpoor-Baltork, I.; Memarian, 1I.R. Synth. Comri~nn.,2000, 30, 551. N-01 I Ph
Ph
DMF , POCb ,90"C
*
q::
Amaresh, R.R.; J'erurnal. P.T. Synth. Corntnun., 2000, 30, 2269.
19%
Fonnation of Aryls
Section 74B
Selvi, S.;
Synth.
Coitiiiiun.,
169
CHO
2000, 30, 3925.
2%PdI2-KI, 100°C
Ph
dimethylacetamide
SH
58%
Gahriele, B.: Salenio. G.; Fazio, A. Org. Lett., 2000, 2 , 351.
Bu M%NC02t-Bu
1. sec-BuLi, (-)-spaitcine, TIIF, -78°C 2. CuCI.2 LiCl, -55°C
* Bo-X0
3.
fiter.
h
I
Me
Me
u; Yu, H. Or$. Lett., 2000, 2, 2283. 'jMq
oTf
&''
N
M
e 64~79%
, CsF , MtCN/THF
10% Pd?_(dha),*CIICl~, 20% dppf 60°C
Yoshikawa, E.; Radhakrishnan. K.V.;
J . Ani. Chciii. SOC.,2000, 122, 7280.
Me, Si
Ph
.$
SiMe,
MeLi , toluene
SiMq Brunette, S.R.;Lipton.
aJ.
Org. C h m . , 2000, 65,S114.
44%
Section 74B
Coinpendiutn of Organic Synthetic Methods, Vol 11
170
Shanna, U.; Ahmed, S . ;
Tetruhedron Lctt., 2000, 41, 3493. 1 . EtNO, , KZCO3 , H2O -6O"C, 1 d
0
2. toluene, i ~ f l u xair , 0
90~53% . . Balllnl.; Barhoni, L.; Bosica. G. J. Org. Chem., 2000, 65, 6261.
phE
P d ( 0 . 4 ~ PPh3, ) ~ ~ CUClz
*
Qy-,
N K2C03.1 d 46% Bt Bt = henwtriazyl Ph Katntzkv..;Zhang, L.; Yao, .I.; Denisko, O.V. J. Org. Chent., 2000, 65, 8074.
I
2% AlCl3 , MtCN ,20"C 65%
t
OH ; Frost, T.M.; Bats, J.W. J . Am. Chent. Soc., 2000, 122, 11553.
Cho, C.S.; Kim, J.S.; Oh, B.11.;Kim, ?'.-J.; Tetruherlron, 2000, 56, 1147.
s PI1
; Yoon,
, Ag2CO&elite
MtCN ,reflux 0 Lee.;Suk,
'
*
J.Y.; Kim, B.S. Org. Lett., 2000, 2, 13x7.
N.S.
57%
@
51%
Section 74B
Fonnation of Aiyls
171
1. HOCHzCOzEt , PPh3 DEAD, T€IF 2. NaIi, THF
c1
NC
C0,Et
*
'-"'*
80x88%
-d NH*
an. A M ; Dumas, J.; Scott. W.J. Org. Ltrt., 2000, 2, 2061.
/-
L
PhCIcII , DCM , sealed tube 5%J GlUbbS' Cakllyd, 40°C
N
Ts-
Ts-
82% (5:ltnei?~Me:orfho Me) Wltulski.; Stengel, T.; Fernindez-Hernandez, J.M. Chenz. Cnnimun., 2000, 1965.
BnNH2, EtNO,, SO2 Ph*CHO
microwaves, 5 min
2.3 N
I
Bn
panu. B.C.; IIajra, A.; Jana, U. Synlett, 2U00, 75.
. R.C.;
51%
Ahmed, S.; Sharina, U.; Sandhu, J.S. J. Org. Chenz., 2000, 65, 922.
ph
PdC12(MeCN),
74%
+
THF , 10°C ~
F
I
,
60%
Ph
Gao, ; W.-Z.; Ying, .I. J . Org. Cheni., 2000, 65, 2003.
1. DCM, heat
2. MnOz, PhH reflux , 4 h
.
.
Kircher, G.; Willems, M. J . Org. Chem., 2000, 65, 2370.
0 53~61%
172
Coinpendiuin of Organic Synthetic Methods, Vol 11
Section 74B
,PhH, reflux Catp-TsOII, 3 h
AcO
Wang, C.;
PhIi, r t , 18 h Org. L.ett., 2000, 2 , 1773. KMnO3-AI2O3, acetone 0°C. I h
McBride, C.M.;Chrisman, W.; Harris, C.E.;
pillladacycle catalyst
Ph
NEt, , T H F , rt
Tetruheclron Lett., 1999, 40, 45.
* ( 3 1 1
83%
Luo. F.-T.;Jeevanandam, A.; Bajji, A.C. Tetruhedrori Lrtt., 1999, 4 0 , 121.
CBH/ = C3EI7 , MeCN 5% Pd(OACX, 5 % ~P(O-TOl),
CsF ,60"C, 4 h
Radhahishnan, K.V.; Yoshikawa, E.; y;bmsm
1.
B-Et
, p h ~ f ~
cat Ni(acac)2/PPhB/A1Mq 2. DBIJ , air
WEt
Mori, N.; Ikeda. S.-i.; Sato, Y. J . Ant. Clieni. Sor., 1999, 121, 2722.
'
Et
Et 60%
Foimation of Aiyls
Section 74B
= =
Bu
173
Bu
5% Pd(PPh3)4, TIIF -van. V.; Takeda, A.a.; Homma, M.; Sadayori, J. Am. Chem. Sac., 1999, 121, 6391.
Kadotn, J.; Komori, S.; Fukumoto,
N/
t-Bu
BU
Bu
Y.;Murai. S . J. Urg. Cliern., 1999, 64, 7523.
1. P h G C H , 2 % PdC12(PPh3)2 1% C U I ,NEt, , 55"C, 2 h 2. lOO"C, 10 CuI , DMF , 1 h 91%
Roesch, K.K.; Lartrck. R.C. Orx. Lett., 1999, I , 553.
MtOII, 50°C
*
/
/
Ph Suginome, M.; Fukuda, 'I'.; Ito. Y. Org. Lett., 1999, 1 , 1077. 0.5
Ph
Nll2
CHO
hv ,PhH , 5 h
Ph Qda.; Nkagami, R.; Nishizono, N.; Machida, M. Chmi. Critnmun., 1999, 2371.
1. THF , t-BuOK , 0°C
2.0.lMIIC1,O"C
&Gee.
u: Leach, J.D.; Setiadji, S . Tctrulierlmrr, 1999, 55, 2847.
86%
Compendium of Organic Synthetic Methods, Vol 11
174
Section 74C
Bu ph-
, THF , 6 0 T
5% S I I I ( O ~ - R3) ~h.
I
*
QEt Ph
c-,"'^px"
Shiraishi, H.; Nishitani, T.; Nishihara, T.; Sakaguchi, S.; Ishii, Y. Tetrulzeilron, I 999, 55, 13957. 1. C&I-13C=CB(Oi-Pr)3, toluene, BF3-OEt2 90°C
Ph
t
2. Li+ , II+
ph
63%
97%
Shen, L. Tetrulidron, 1999, 55, 14235.
Brown, C.D.; ;M.. J-
PhS02(CII2)SMe, ??IF BuLi ,PhCOCl, I-BuOK -78°C Orita, A,; Yaruva, .I.;
.-, It
75%
reflux
4
Angew. Cliein. Int. Ed., 1999, 38, 2267.
."
Et,Zn, toluene, -35"C, 3 h 1.2%Cu(OTf),
1.3%~ c h i d phosphoramidate ligand
Mandoli, A,; Arnold. L.A.; de Vries, A.H .M.; Tetruhedr-on A .synini., 2001, 12, 1929.
Et,Zn , toluene , -20°C
89%ee,R
-8.
4% c h i d diunine-carhene ligand
%/,
Et 92% (22% ee, S) Guillen, F.; Winn, C.L.; Alexakis. A. Tetruherlron Asymni., 2001, 12, 2083. 4% Cu(OTf), , 2 h
R
0
Et,Zn , toluene , 0°C 2% silver diamino-cailwne 2% Cu(OTf),
a
98% (23% ee) Pytkowicz, H.; Roland. S.; Mangeney, P. Tetruhorlmn Asymm., 2001, 12, 2087.
PI1
Tong, P.-E.; Li, P.;
Ph
&.
EtJn , chiial unino-alcohol MtCN, -3o"C, 12 h
* Phu
p
h
89% (82% ee, S) A S'.C'. Tctrul7erlron Asyrizni., 2001, 12, 2301.
Section 74E
Conjugate Alkylations
197
c
Jha, S.C.; Joshi. N.N. Tetruhcrlmn A s y i i m . , 2001, 12, 2463
Et,Zn , 2% Cu(OTf), , 16 h 4%phosphonite ligiuid toluene, -30°C
quant (41% ee ,R )
% " ,,
Et Tetrulicdmn Asyinnz., 2001, 12, 2497.
;-
1,
. T
Ruiz, A,; Claver, C. Teti-uhcrlron Asyinni., 2001, 12, 2861.
15%L-prOli~e NO2
x e tone, DMSO, rt
NO2
h s t . B.; Pojarliev, P.; Martin, 11.1. Oq. Lett., 2001, 3, 2423.
97% (7% ee)
his-oxawline ligandKh(OT1h 1-1 PI1
Zhuang, W.; Hansen, T.;
Id Chciii. Coiiiimin.,
73% (60% ee) 2001, 347.
Coinpendiuin of Organic Synthetic Methods, Vol 11
198
Section 74E
MeOzC 1.3 Mg(C10,)z ,EtI l 0 q Bu3SnH, DCE
)-.”’
- Hbo
BEt3,Oz. his-oxamline -78”C, 3 h (2- naph th)
(2-naphth)
79% (84% ee) Angew. Chein. Int. Ed., 2001, 40, 1298.
Nukamura, I.; Oh, B.H.; Saito, S.;
, 0.15 AgOTf, H20
C02Bn
0.1 R-Tol-BINAP ,0°C 94% (56% ee) Kohavashi. S , ; Kakumoto, K.; Mori, Y.; Manahe, K. Isr. J. Chein., 2001, 41, 247.
0
. DCM, 10h chiral Ru complex , KOH
/-l-
Suzukl.;Torii, T. Tc.truhedrrin A.syiriin., 2001, 12, 1077. Et,Zn, Cu(0Tf)Z , DCM chiral xylofuraciose ligand 92% (60% ee) rt,lh
Et
P\am.les.,Net, G.; Kuiz.;Claver, C.; Woodward, S. Tetruhadron Asyrnm., 2000, 11, 871. Cu(OTf)2-chiral phosphite oinplex Et2Zn, toluene, 0°C , * 3h Yan, M.; Zhou, Z.-Y.;
tL
Llhan. A.S.C. Ckiiz. Cnnrrizrm., 2000,
115.
quant (73% ee)
e
199
Conjugale Alkylations
Section 74E
94% (64% ee)
Tomioka.; Nakagawa, Y. Hcterocyles, 2000, 52, 9s. Et2Zn, Cu(OTQ2 , blueiie chiral quinoline binaphthol ligand -15"C, S h
4?A Ph
Et :. Tetruhedron Asymm., 2000, 11, 2387.
dolle,I-
Arena, C.G.; CXahrb, G.P.; Francib, G.; F;rr
Ph
(i
96% (70% ee)
-WC Et2zn, 2 . m cU(o'rq2, 5% chiral phosphomnidite toluene
*Phu
p
Arnold, L A ; Zlnlios, R.; Mandoli, A.; de Vries, A.H.M.; Naasz, R.; m Tetruhedron, 2000, 56, 2865.
Et,Zn , 3 % Cu(O'TQ, , toluene, 15 h cat c h i d oxmline-phosphik ,-20°C
c
*
Escher, 1.1-1.;&lkA Tetruliedron, 2000, 56, 2879.
h
85% )89% ee) a . B.I..
bEt
99% (up to 86% ee)
2 HI EtllZn , chiral QIJII'IIOS catalyst 0.5%CUI , DCM , 1 1 2 0 ,-20°C
Delapiene, G.; Constantieux, T.; Brunel, J.M.; Buono.
76% (61% ee) Et
Compendium of Organic Synthetic Methods, Vol 11
200
Section 74E
CH2(C02Bn)z, 0°C ,45 h
53% (85% ee)
La-linked-BINOL coinplex
C H(CO2Bn)2
a
Kim, Y.S.; Matsunaga, S.; Das, J.; Sekine, A.; J. Am. Chenl. SOC., 2000, 122, 6506.
Ph
Et,Zn , MeCN ,-30°C Ni(a c a ~ ) ~
Ph
chiral thioether alcohol catalyst
Phu
p
h
94% (60% ee) Yin, Y.; Li, X . ; Lee, D.-S.;Yanc. T.-K. Tetruherlmn Asynln~.,2000, 11, 3329.
Schneider.;Reese, 0 . Synthesis,
PhBs
2000, 1689.
1. BuLi 2. B ( 0 M e h 3.
n (
Takaya, Y.; Ogasawasa, M.; Hayashi, T. Tctrulicrlron Lett., 1999, 40,6957.
4
-Ai
1. cat. Ni(acach(chisal oxuolidine) M q Z n , TMSCl , tiiglyine
ECsCEt
2. H?O+
78% (81% eel Beds. S.-i.; C h i , D.-M.; Sato, Y. J. A I I LChw1. Snc., 1999, 121, 4712.
Et
Et
Section 74E
Conjugate Alkylatioris
EtzZn, 1 % Cu(0Tfh
201
?L
quant (90% ee ,S)
2% chiral aryl diphosphite tolucrie ,0°C , 1 h
S . C . Tetrulicdron Lett., IYYY, 40, 6645. S @-Tol)BINAP, 5% CUCl
COzEt
Ph
COzEt
10% NaOt-Bu, rt , 1 d pol yinethyl hydroiloxarie
84% (90%ee)
Applla, D.H.; Moritani, Y.; Shitani, R.; Ferreira, E M . ; B u c h w u J. Aiii. Clieiii. Soc., IYYY, 121, 9473. 0
PhB(0Hb , 3 % Rh/S-BINAP water , dioxane , 100°C
II
94% (96% ee, S)
OEt
IIaYdhhl..; . ,. Senda, T.; Tukaya, Y.; Ogasawara, M. J . Ani. Cliern. Soc., 1999, 121, 11591. Et,Zn, 1% Cu(OTf), , 0°C 2% chiral aryl diphosphi te quant (90% ee)
toluene, 3 h
Et
Yan, M.; Yang, L.-W.; Wong, K.-Y.;
Li[PhB(OMe)J CQMc
q dioxane , 3 h
3% R h(ac ac &I
-tie
, 100°C
i&S-B INA P
Takayn, Y.; Senda, T.; Kurushima, H.; Ogasawara, M.; Havashi. T, Tetruhedron Asyniiii., I Y Y Y , 10, 4047.
Hu, X.; Chen, H.;Z h a n l . . r i g c , w .
Cheiii. b i t .
C02Me
Ed., l Y Y Y , 38, 3518.
>99% (89% ee)
'gMe2 $
Section 74E
Compendium of Organic Synthetic Methods, Vol 11
202
chird R u complex ,DCM , KO13 ,10h
u; Torii, T. Tetrulicdron
suzu
s '
\ Asyiirrii.,
>99% (75% m ,S)
2001, 12, 1077.
NON-ASYMMETRIC ALKYLATIONS
COlEt
Tateiwa, J.-i.;
CqMe
a
,140"C,6h
-k COzEt
0
96%
Eur. J. Org. Chcwi., 2001, 1445.
97%
IIuang, T.-S.; Li, C.-J. Chcwi. Conrrnun., 2001, 2348.
--?
COzMe a t Cu(OTf)(his-oxamline), DCM , -78"C, 2 h
pfi
Jensen, K.BV.; Thorhauge, 1.; Hazell, R.G.; Angew. Chani. Irrt. Eli., 2001, 40, 160.
quant (88%)
Section 74E
Conjugate AIkyIations
0.1%[RhCl(cod)]2 , 9 0 T
1
203
P-TOl
I120
TolB (0H)z , 6 h Cheni. k t t . , 2001, 722. PhSIlMq ,H20,5O"C, 12 h
-Co2Et
COzEt
5% [Rh2(&)2~21
65%
Venkatraman, S . ; Meng, Y.; J .i. C.-L Tctruhedron Lc.tt., 2001, 42, 4459.
&SiM%
0.1 ItlC13
5 eq TMSCl , DCM
':?@
Lee. P.& Lee, K.; Sung, S.-y.; Chang, S. J . Org. Cheni., 2001, 66, 8646.
PhSnMq , 2h
ca t [ Cl(cb 96%
Bu
-
>.
Zinn, F.K.; Kamos, E.C.; Comasseto, J.V. Tetrulzedl-on Lcjtt., 2001, 42, 2415.
0
COZEt , h v
CO$t
benzophenone, 2.5 h
70% (1.33:1 E:Z)
W.& IIannan, J.J. Tetruherirnn k t t . , 2001, 42, 3211.
Bu,N Ph3Sir;? , TI-IF
c02et
*Co2Et MS ,7S"C
Xuan, J.X.; F&yJ-L
Tetruherlrnn Lett., 2001, 42, 3275.
c02et
74% (7:l E:Z)
206
Compendium of Organic Synthetic Methods, Vol 11
TBAB , HCOzNa , PhBr , 130°C
C02Me
Ph%
Section 74E
LP
cat Pd-hithiazole coxnplex , NaHC03* ph
Calb. V.; Nncci, A.; Lopez, I.,.; Napola, A. Tetrcrhedron Lett., 2001, 42, 4701.
T
O
L
Pastor, I.M.; LuJyf..
i
1.
D
77%
o ,TI-IF
2 eq CuI , HMPA -78°C 2. NH4Cl Tetruheclron, 2001, 57, 2311.
(95 Giuseppone, N.; C o l l l n . T e t r u k d r o n , 2001, 57, 8989.
70%
5) quant
J(.InC13 DCM, r t , 3 h
ir
*o
H ._ Yadav. J.S.; Ahraham, S.; Reddy, B.V.S.; Sahitha, G. Synthesis, 2001, 2165.
+
Ph
C
N H , f r 2 0 , 21nin
Ph
micmw aves
PhU p : % m g h a d d a m . F.M.; Mohammadi, M.; IIosseinnia, A. Syntlt. Comrnun., 2000, 30, 643.
Section 74E
207
Conjugate Alkylations
CH2(C0,Bn), , THF , 0"
53%
45 h , polymer-hound
La-BINOL catalyst
Matsunaga, S.; Ohshhna, T.;
'
C02Br Tetrulmlron Lett.. 2000, 41, 8473.
0 Bennahi, S.; Narkunan, K.; Rousset, L.; Bouchu, D.; Ciufolini. M .4 . Tetruh~~ilrori k j t t . , 2000, 41,8873.
0
Et,Zn , l%Ca(OTf), 2.5% aminoethyl[ hosphiiies DCM , 0°C , 5 h
Morimoto. T.; Yamaguchi, Y.; Suzuki, M.; Saitoh, A. Tctrulterlron Lett., 2000, 41, 10025.
I
ZnEt, , 2 . 5 eq CuCN, 0°C
99%
NH(Bn)SO#h, toluene, 1 h
Kitdmurd.; . . Miki, T.; Nakano, K.;
Et B i d . Chenz. SOC. Jpn., 2000, 73, 999.
, d ,DMWPy
0.13 CoBrz + 0.26 hpy , 70°C-
E 0,C
Gomes, P.;
; Ntidtilec, J.-Y.; PCrichon,
64%
J. Tetrulieclron Lxtt., 2000, 41, 3385.
Section 74E
Compendium of Organic Synthetic Methods, Vol 11
208
Ph4Sn, cat PdC12,2 eq LiCl
Ph
AcOH , air, 25"C, 20 h
0
81%
Ohe, T.; Wakita,T.; Motofusa, S.-i.; Cho, C.S.; Ohe, K.; 1Jemura. S, Bull. Cheni. SOC. Jpn., 2000, 73, 2149.
@
,DMF
1.
do
0
Ac
Pd(OAc)z, KOAc
c
2. H2 , 5 % P d K , EtOAc
0
64~95% 0 Arcadi. A.; Chiarini, M.; Marinelli, F.; Berente, Z.; Kollhr, L. Org. Lett., 2000, 2, 69.
2
PhI, Pd(OAc)z, NEt3 , X0"C 100 bar COz (supeiu3ical)
*
, Ph .
88% Ph
CJtchl.;Fabrizi, G.; Gaspairini, F.; Pace, P.; Villaui, C. Synletr, 2000, 650.
0 1
2. CH,=CIICO~M~ 150 W lamp, 10°C
Ollivier, C.;
*
Ph
'es-
1. catwhohora1e ,Cat Me2NCOMe
NO2
N- OCOzMe
70%
Angew. Cliern. Int. E d , 2000, 39, 925. Et,Zn, 0.5 Cu(OTf), ,-30°C 1% c h i d P ligand , toluene
Bexakis. A,; Benhaim, C. Org. Lett., 2000, 2 , 2579.
Illraa.;Takada, 'I'. Sakurai, ; 11. Org. Ixtt., 2000, 2, 3659.
*
L
Ph
N
0
2
quait (64% ee)
Section 74E
MeO2C
Conjugate Alkylations
209
PhB(0Hh , aq MeOII ,25"C
-C02Me
4% [Rh(codXMeCNX]BF~, 6 h
Sakuma, S.;Sakai, M.; Itooka, R.; M
a J.
COzMe
M~O~C 84%
Org. Chem., 2000, 65, 5951.
syringe pump (14 h) COZEt
49%
U;Kim, S.K.; Kim, J.Y.; Lim, J . Tetr-uhedmn Letf., 2000, 41, 5915.
3%
58% (1:99 ~ n t i : ~ y n )
IIayen, A.; Koch, K.; Metzeer,.Arigov. Clicm h i t . Ed., 2000, 39, 2758. PhCIIzBr, 2.1 4 CrCI,
*
Mn , THF , 4 . 2 eq 4-t-Bu-piperidine ,4u&.
L; Gil, R.; Kalsey, S. Tetruli~ilronLett.,
ZYYY, 40, 67.
- _.
Phc-N 85%
Kumar.;Keddy, B.V.S.; Keddy, P.T.; Yadav, J.S. Tctruherlron k , t t . , ZYYY,
a
40, 5387.
1. o ( ' : ,B 10% MezNCOMe r l 0 DCM , heat, 3 h 2 . 3 q I I 2 0 ,DMP'CJ , DCM ,Oz
Ollivier, C.;
' Cherri. Eiir. J.,
I Y Y Y , 5, 1468.
86%
Compendium of Organic Synthetic Methods, Vol 11
210
Section 74E
0
da Silva, F.M.; Comes, A.K.; Jones Jr. J. Cun. J. Cheiii., 1999, 77, 624. Bu,GaLi ,TIIF, 0°C + rt
Ph?ph Han, Y.;
*
0 1.
phnphBu
Y . - Z ,Fang, L.; Tao. W.-T. Syntlz. Commun., 1999, 2Y, 867.
EtzNTMS ,50"C, 16h
I
CHO ; Ono, H.; Kornatsuhara, N.; Hoshi, T.; Suzuki, T.; Ando, M. Tetruhedron Lett., 1999, 40, 6627.
C02Et
78%
0
51%
5.5% bis-oxamline , 5 % Mg(0Tf)Z 6% NMM ,CHC13, MS , tt p,,+
CO2Et
JiJ; Barnes, D.M.LZhang, J.; King,
95%
S.A.; Wittenherger, S.J.; Morton, H.E.
J. Ant. Chern. Snc., l Y Y 9 , 121, 10215.
Bosco, M.; Bellucci, M.C.; Marcantoni, E.; Sambri, L.; Torregiani, E. Eur. .I. Or%. Client., 19Y9, 617.
;-
REVIEWS: "Catalysis of the Michael Reaction and the Vinylogous Michael Reaction by Femc Chloride Iiexahydrate," Christoffers. J. Synlett, 2001, 723.
Section 74F
21 1
Cyclopropanations
"Rhodium Catalyzed Asyimnetric 1,4-Addition of Organoboronic Acids and Their Derivatives to ' Synlett, 2001, 870. Electron Deficient Olefins," "Vinylogous Mannich Reactions. Seiectivity and Synthetic Utility," Bur, S.K.; Tetruhedron, 2001, 57, 3221. "Intramolecular Free Radical Conjugate Additions," Zhanc. W. Tetruhedron, 2001, 57, 7237. "Recent Advances in Catalytic Enantioselective Michael Additions," Krause.;Hoffmann-Riider, A. Synthesis, 2001, 171. "Reactions of Conjugated IIalocnoates with Nucleophilic Reagents," Caine. D , Tetruhcdron, 2001, 57, 2643.
SECTION 74F:
Cyclopropanations, including Halocyclopropanations
\
(i-Bu),Te
:
8) 83%
SiMq
Ye, S.; Tang. Y.; Dui, L.-X. .I. Org. Ch~rii.,2001. 66, 5717.
87% (96% de, 89% ee) Davies. H.M.1,; Townsend, R.J. J. Or#. Cliein., 2001, 66, 6595.
1. LiHMDS ,TIIF 2. cat c i r v r m
PhN'-Nksr
5
CI-I,=CII-NPhTh
Ph
0
71% (33:67 truns:cis) V . L ; de Vincente, J.; Connert, R.V. Org. Lett., 2001, 3, 2785.
212
Section 74F
Compendium of Organic Synthetic Methods, Vol 11
lo
1. Et02CCH2NH2*IIC1,TPPRh(1II) DCM ,HZO, -10°C
Ph-
Ph
2. NaN02, aq H$S04, rt , 4 d
CO2Et 62%
Barrett.;Braddock, D.C.; Lenoir, I.; Tone, H. J. Org. Chem., 2001, 66, 8260.
-
3 q Zn(CH21)2 , DME DCM, -10°C rt
Et*c3 Me?NOC,r,, n -
Et
B u
*
"tMo
Et
69% (86% ee)
MQNOC
C ~ W ~ A L A Jolicoeur, .B.; E.; Bydlinski, G.A.S. Org. Lett., 2001, 3 , 3293. CEIN2
RU catalyst pentme
90% (74% ee)
0
Barheris, M.; Perez-fieto. J, ; Stiiiha, S.-E.;
Org. Lett., 2001, 3 , 3317.
-* 4 ,
NC -.%Me3
SiMe,
1) 2.3 eqBuLi
2, L
B
r
65% (>98:2 E:Z)
3) H 2 0 Lnnger. P.; Freifeld, I. Org. Left., 2001, 3, 3903.
Me2
2. 1 .TfiO, 5 eq Dibal -78°C
Ph
2,6-lutidine
"%,p
fr 86~73% Et02C?3 Tavlor.;Engelhardt, F.C.; Schmitt, M.J.; Yuan, H. J. Am. Chem. Soc., 200Z, 123, 2964. Ph
Et02CCH=N2
-
A C 0 2 E t Ph tiis@ yr Lwly1)borate"opP"lf1) catalyst Diaz-Requejo, M.M.; Belderrain, T.R.; Trofmenko, S.; PBrez, P.J. J. h i . Cherli. Soc., 2001, 12.3, 3167. Ph-
97%>98:2
Section 74F
Cyclopropanations
Charette. A,]&; Bcauchemin, A.; Rancoeur, S. J. Ant.
Clieiii.
=
80°C
Furstner.;Stelzer, F.; Szillat, 11. J.
-
h i .
SOC., 2001, 123, 8139.
T s ,
10% RC12 , toluene
Ts-N
213
Q N
59%
Chtrrr. Snc., 2001, 12.3, 11863.
Ssha, B.; IJchida, T.; Katsuki. T. Syntott, 2001, 114.
N2C€IC02t-Bu,Co(1I) complex
A
Ph
MeOH , 5 % )1 1 2 0 , 50°C
4 C 0 , t - B ~ Ph
80% (83: 17 trcms:cis), 92% ee Ikeno, T.; Nishizuka, A,; Sato, M.; Yalnada. T. Synlett., 2001, 406.
1. Me-
IPh' OTf
NHSo2Ph
BuLi , TIIF 2. I N HCI J,ec. II.-Y.; Lee, Y.-11. Synletf, 2001, 1656. NZCHCO2Et. rt \ - hP
*
0
55%
phb
Ru catalyst, 2,4,6-~llidine
0,Et
-I-PhmO,Et
(30 70) 81% 70% et: 82% ee Zhene.; Yao, X.; Li, C.; Chen, II.; Hu, C. Tttr-uhedmn Lett., 2001, 42, 2847.
section 74F
Compendium of Organic Synthetic Methods, Vol 11
214
do
0
Metal salen catalyst, 1 d
-cl+
NMI ,'ITIF, rt
-
72% (98%ee) C1
CJchida, T.; Saha, B.; &&&J
'
T~tmhedmnLett., 2001, 42, 2521.
Tetrulierlrnn Lett., 200I, 42, 3369.
Fujiwarn, T.; Odaira, M.;
A
Ph
B
Me,SiCIIN2 , DCM , -20°C t [ RUZ(CO)7( p-OAC121
ph\a/siw3 +
SiMe,
68) 64%
(32
Maas.;Seitz, J. Tetrulwdron Lett., 2001, 42, 6137.
CIZCNCO2Me, 1,iHMBS THF , DBlJ
Escnbano.; .. Pedregal, c.;
; Fernhndez, A.; Burton,
a
62%
K.; Stephenson, G.A.
T(~truheclron.2001, 57, 9423.
+ \
Ph
N,CIICO,Et, DCM
c h i d Ru d e n catalyst
Yao, X.; Qiu, M.; Lu, W.; Chen, 11.;
*
4-
PhmCQ2Et
C0,Et (26 74) 82% 44 %ee 43% 133 Tctmhedron Asymitt., 2001, 12, 197.
Section 74F
Cyclopropanations
215
N,CI-ICO,Et, Cu(L)(OT!)
PhA \
L = dirunino biphenyls
*AT
COzEt
Ph
94% ( 8 4 18 hun.s:cis) (46% ee 57% ee) Sanders, C.J.; Gillespie, K.M.; Scott. P, Tetruhedron Asymnz., 2001, 12, 1055.
A \
P11
N2CMC02Et, Cu(OTfh [emiin] NTf2 chiral his-oxawline
- A Ph
CO2Et
38% (64 : 36 truns:cis) 6 0 % ~64%ee Fraile, J.M.; Garcia, J.I.; Herrerias, C.I.;m o r a l . J.& CaTie, D.; Tetruhedron Asyiiini., 2001, 12, 1891. in ionic Iiqluid
A \
N,CIIC02Et, Cu(1)khird runine
Ph
CI-ICl, ,reflux
m d C D z E t 61% (3753 cis:truns)
3 6 % ~40%ee Ma, .I.-A.; Wang, I-.-X.; Zhang, W.; a o u . 0_.-Id. Tetrul7erlron Asyntni., 2001, 12, 2801.
Q0
toluene, 200"C, 2 d scaled tube
I 0
I4
; Ishigedani, M. Tefrukcdron. 2001,
fI i
0
I
N
CQEt
COzMe
Ph 57, 2589.
1. MqSiCHNz -1 00°C
2. ultra.sound AgC0,Ph
*LA 0
C02Et
I
53x54% CO,Me &uU. 1 G . C Saint, R.E.; Saint, S.L.; Chamhers-Asman, D.M Synthesis, 2001, 247.
Li , T H F , -78°C. 3 h
44'-di- terf-hutylhiphen yl
+NHOMe
Yus. M.; Radivoy, G.; Alonso, F. Syntlwsis, 2001, 914.
A
0
CII,(CN)2 , KOII , DCM
NI IPh
Bu,N €KO, ,i t , 3 h
Dave. C . G ; Parikh, V.A. Syntli. Corrititun., 2001, 31, 1301.
dN
0A N/z NH~ I
I
Ph
60%
Amides from Anides
Section 81
1
3eq
231
s\\ PEt @ N A H
-
95%
N ' Me2 200"C, toluene, 15 mill Ph microwaves Lev.; Leach, A.G.; Storer, K.I.J. Clieni. Sor., Perkin Truns, 1, 2001, 358.
Ph
NMe,
se r'il
4 q rncpba , 8 eq NaII
i-PiOoII ,rt N MBz Ward. V.R.; Cooper, M.A.; Ward, A.D. J. Chern. Soc., Perkin Trans. I, 2001, 944
B toluene, u 3 s n Hreflux 3 J 3 N _ I1
&;yJL;h
54% El Bialy, S.A.A.;Ohtan, S . ; Sato, T.; Jkeda. M . Hoterocyclcs, 2001, 54, 1021.
Is.
'*
5 eq L D A , ether 'I'sIIN N &
-78°C
Arjona, 0.;Menchaca, R . ;
85%
27%
2-R +
a I Hcrorocycles, 2001, 55, 5 .
60%
Bothe. U.; Rudheck, 11.C.;Tanner, D.; Johannsen. M. J. Chern. Soc., Pcrkin Truns. I , 2001, 3305. N -Ts
MeMgBr , 'lI~IF-t(>lUel1e chiral Cu catalyst , 0°C
Muller.P.; Nury, P. Hdv. Cliini. Actu, 2001. 84, 6 6 2 .
N HTs 52% (91% ee)
Compendium of Organic Synthetic Methods, Vol 11
23 8
Section 8 1
*A Ts
PhCI-kN-NTC Na' , 1%Rhz(OAc)4
P hCII=N-Ts
20% sulfide,40"C , dioxane 10%chiral BnNEt,Cl
Ph
4%,*
Ph
68% (2.5:1 1runs:cis) V . L ; Alonso, E.; Fang, G.; Ferrara, M.; Hynd, G.; Procelloni, M. Angew. CIIW. rrrt.~ d .2001, , 40, 1433.
L
BnO
'c
-78°C
'-t
0
Lindstriim, 1J.M.;
' '
p+ 6
2 eq LiIIMDS , DCM 12
85%
CIz~nr.Eiir. J., 2001, 7, 94. , BF,*OEtZ Ph
PhA
N\
Ts
Ungureanu, I.; Klotz, P.;
-
1111l11l11
DCM ,-78°C
TsHN
Ts (1 . 1) 45% Angcw. CIiem. Int. Ed., 2000, 3Y, 4615.
Ph
GNL
1 . B uLi , TI-IF , -78°C
2.-78"C
'-t
It
*
/ A Br Ph Ph 98% (9.8:l de) He, S.; Kounin, S.A.; Rawal. V.H. J. Am. CI?em.Snc., 2000, 122, 190.
Frank, K.E.; Auh6. .I. J. Org'. CIiern., 2000, 65, 655.
Section 81
Aniides from Anides
239
/o-””
6 02s
I
02s
PhSnMq , LiF , 110°C
I
*
3%) R ~ ( x x ) ( C , I I ~ ~ 6% R-MOP , dioxaie , 10 h
FF
s . .. Ishigedani, ; M. J. Anz.
F3 CI7~~1ll. Soc.,
c
2000, 122, 976.
5%) TBAF, T I I F , 4 h
N-Ts
>99%
M q S i N , , rt
Wu, J.; HPU. X.-L; Dai, L.-X. J. Orx. Chelii., 2000, 65, 1344.
NI ITS
5% TiC14 , CHCl, SiMe2Bn
rt,3.3 h
93%
Miura, K.; Hondo, T.; Nakagawa, T.; Takahashi, T.; IIoso
78% (54:46 cmti:syn)
1
.
urd2.; . Trogolo, C.; Umani, I;. Org. Lett., 2000, 2, 401. 3
PhS0,NIIEt Katohgi, M.; Yokoyama, M.;
PhI(OAch, 1 2 , I X E , 3 h t
ultrasoutid ,40°C Synlett, 2000, 1055.
PhS02NH2
71%
Section 81
Compendium of Organic Synthetic Methods, Vol 11
240
t-BuSOCl , DCM i-Pr,NEt, (PhSc), rt
-5O"C-,
*b
+
S
e
€
h
59%
Lin, X.; Stein, D.; Wcinreb. S.M. Tetrulicdron I x t t . , 2000, 41, 2333.
@ CI - b - = N
0
Bn
'
90%
BF3-OEt,, DCM
Bn
Bt = benmtiiazol-I-yl Mehta, S.; IIe, H.-Y.; Cui, X. J . Org. Clierri., 2000, 65, 4364.
N-SO2Ph
II
NHSO,Ph
PhMe,SilI , 10% B(C,F,),
AII
b
toluene , rt , 3 0 inin PhA 1 3 93% Ph 11 . Blackwell, J.M.; Soninor, E.R.; Scoccitti, T.; Piers. W . E Or8 k i t . , 2000, 2, 3921.
m
PhA ' N -SO,P h
B
r
,In
NIISOzPh
THF Lu, w.; cilaLuL J. Org. Cliern., 2000, 65, 8589.
'
Ph
v M&
2.5
N -Ts
99%
Ph
MqSiCH=Nz 72% ( 9 5 5 cis:trans)
dioxme ,40"C
cat [Kh(cod)MeCN),]BF~ , dioxane
2.H20
IJeda, M.; Snito, A,;
I
)r
Me0 Synkrt, 2000, 1637.
Section XI
Anidcs froiii hrnides
241
Me
I
Me
I
BF3*0Et,, toluene inimwaves 54-56°C
1 ) >99%
(999 Cardillo, G.; Gentilucci, L.; Gianotti, M.; Tolornelli, A. Synlett, 2000, 1309.
Wu, Y.-L.; Chuang. C.-P.; Lin, P.-Y. Tc~truhedr-on,2000, 56, 6209.
-1,
O Y T B n
2'Me1
0
+
(&f'T0x7 "'%,,,,
1 . LHMDS , - 78°C
-
(93
o&
Bn
Bn
7) 65%
JqB
Bull, S.D.;m e s . S.G,; Nicholson, R.L.; Sanganee, H J . ; Smith, A.D. Tetruherlron A,~yiiiiri.,2000, 11, 3475.
llrLB*' 0
0
COZMe
3 eq A d N *I
Na(0AchBH. MS 4A DCE, 15 h , 0°C -.+ rt
0
Ph
Beshore. D.C.; Dinsmore, C.J. Tetrulicdron Lett., 2000, 41, 8735.
64%
Compendium of Organic Synthetic Methods, Vol 11
242
Et,Zn ,Cu(OTf), ,toluene
Section 81
98% (93%ee)
Ph-N-Ts
chirlll phosphine ligand ,02 Ph J. Am. Chern. Soc., 2000, 122, 12055.
Fujihara, H.; Nagai, K.;
PhSi(OMe)3, DMF Cu(O A C ),~it
+
61%
0 0 P.Y.&; Deudon, S.; Hauptinan, E.; Clark, C.G. T~~truhcdron Lett.. 2000, 42, 2427. Me&
TOO,\
Me,SiCIIN,
Ni Ph 3h
N-SOZTol
Ph
75%
Tetruhedron L.ett., 2000, 41, 9455.
Mori, R.;
jiNlih a9shyf:urai Cxo's ackl/Si02, MLCN
Ey10 v ,Ph ,.'
'
. ... .
. M.M.; Ghodrati, K. Syntlt.
* Ph Cornnlrm.,2000, 30, 2353.
*li:
, 3 % Pd(PPh3)4,THF
F hCH=NTs
rt,lh
96%
Ph- " K O B n
TBN,DMF, 23"C, 5 h
0
Salvatore, R.N.; Shin, S.I.; NagIe, A.S.; Junp K .W. J. Orb. Chem., 2001, 66, 1035.
Tr
\
N
(>\/oms
TFA, Et3SiI-1, DCM l h
H
\
= - N
&oms
Y~QSJL;Klapars, A.; Warner, D.L.; Weiss, A.H. J. Org. Chem., 2001,66,7542. Ph2C =N-OH
f-BuSOzCl,ether, NEt3
-35°CI't Artmann 111, G.D.; Bartolozzi, A,; k k . R.W. : W&eh.
t
85%
P h2C=N S O f-Bu
S.h.I. Synlett, 200Z, 232.
Arnides from &nines
Section 82
241
PhCI-I(C0zEt)2,mimwaves PhNI-Iz
83%
15 inin ;- .
0 Veiveer, P.C.; Osnahrug, S.J.M.; Visser, G.M. Tetrulzerlron I A t . , 2001, 42, 1367.
0
H
6 '' 1
1. NaIIMDS ,THF
I F
3
C
v
0°C + I t , 2 I1
N
H
*
z 2. PhCOzMe
Ii&
94%
0
Wane.; Rosingana, M.; Discordin, R.P.; Soundararajan, N.; Polniaszek, R. Synlett., 20191, 148.5.
1, o
NIIz
l r ~ o z c N i m
NEt3 , CHzClz , 20 inin
* e N " N H I1 2
2. H2/Pd , AcOII
Liu, Q.; Luedtke, N.W.;
NI 12
Ph
92%
m.Tetrulwlron LL)ft.,2001, 42, 1445. 1. C S ~ C , O ~ , Me1 ,23"C TBAI, DMF
2. BnBr , Cs2C03 87%
Salvatore, R.N.; Ledger, J.A.; Junrr. K.W. Tetrulzedron Lett., 2001, 42, 6023.
I Me
OB n
Ly
VomDMs DME , acetone, CO
N
OTBDMS
4 h , 100°C 0 quant cat co2(co)8 Bn Davoli, P.; Forni, A; Muretti, I.; Prati.;Tome, G. Tetruliedr-on, 2001, 57, 1801.
I
PhCIIzNIIz
BnBr , CO2, DBU , I 1 2 0
BnNIICOzBn 6%
u; Shen, Y.-M. Helv. Cliiiit. Actu, 200Z, 84, 3357.
+
PhCHZNBnz 60%
Coinpendiuin of Organic Synthetic Methods, Vol 11
248
C3€I+202Me,hexane mninocyclau: I , rt
Youshko, M.I.; van Rantwijk, F.;
6
Section 82
-
Tctrultd-on Asyninz., 2001, 12, 3267.
-6
98% IICOzN , 100°C , 3 h
72%
N€Iz N I ICI10 Chakrnharty. M.; Khasnohis, S.; IIaiigaya, Y.; Konda,Y. Syntli. Cominun., 2000, 30, 187.
/ '
II
iiuciuwaves , 10 inin
kl
\/
I .
3
:
0 .I? Satti, .; N.K.; Suii, K.A. Synth.
,c
Feroci, M.;
N-
i-Pr
2000, 30, 3709.
-
2. coz 3. EtI
Inesl.;Rossi, I..
84%
NEt,' (via electiulysis)
1.
C6WIlNHZ
Coniiiiicn.,
I
C$iiNHCOZEt
-c
Tcrruliedron Lett., 2000, 41, 963.
AcZO , 120"C, BF,*OEtZ
80%
N-Ac
14 h
76%
P.K;Kuinar, K.A.; Duddu, R.; ; Dai, R.; Das, K.K.; Gum, X.-P.; Sun, J.; . . Trlvedl.; Gilardi, R.D. J. Orx. C h ~ n .2000, , 65, 1207.
bIlph
Br
Br>drph
TMSO
Bandini, E.; Favi, G.; Martelli, G.;
heat, toluene overnight
##
40%
0
. Pieisanti, G. Org. Lett., 20U0, 2, 1077.
Section 82
aa,
249
Anides from Amines
0
2. -Br
N
In,DMF,16h
75% (30:70)
CO2Ph
Lab. T.-P.; Lye, P.-L.; Wang, R.-B .; Sim, K.-Y. Tetruherlrnn tctt., 2000, 41, 7779. 1.5g HCO2NH2
-
PhNHCHO 96% MLCN , E t l u x , I l h Reddy, P.G.; Kuinm, G.D.K.; Baskaran. S. Tetruh~clronk t t . , 2000, 41, 9149. PhNH,
I N
1. BuLi, THF, -45°C 2. 1 atin C O , -45°C + -30°C
-
L-
3. sutd aq NH,C1 -30°C 20°C
/
I
84%
Me0
Me 0 Iwamoto, K.; Chatani, N.; Murai. S. J. 01-8.Chern., 2000, 65,7044. ,CY 2% Ru3(CO),2 , 2 atin C O , 20 h
71%
toluene, 160°C 0 -
Kamitani, A.; Chatani, N.; Morimoto, T.; m a i . S, J. Org. Chetlz., 2000,65,930.
i\,,,
(Me0)2C=O9Y - A I ~ O ~
4.
85% Ph wflux, 2 d Ph CHCOZMe Vauthey, I.; Valot, F.; Gozzi, C.; Fache, F.; Jxrnuue. M. Tl,ti-uhedronLett., 2000, 41, 6347. Ph
NH2
C,FS(Me)NC02Ac, THF
Kondo, K.; Sekiinoto, E.; Nukuo, J.;
rt , Soinin
*
NHAc
Ph95%
Tetruhedron, 2000,56,5843.
250
Section 82
Compendium of Organic Synthetic Methods, Vol 11
.
.
Tanirnon. S, ; Kisihata, M. Tetruhedron Lett., 2000, 41, 6785.
KMn04 , DCE ,reflux, 6 h C - P h
B nNEt,CI
co 67%
N-Ph
* MdThtTrlf.; . Stickney, C.A. .I. Heterocyclic CIieni., 2U00,37, 109. 1 .
70%
17) 93%
(83
Davoli.; Prati, F. Hr.terocy1e.T. 2000, -53, 2370. BnCl , K 2 C Q ,596 Bu4NBr, 2 h F MqNC02Bn onium salt , supesciitical CO, 80 at111 , 100°C Yoshidd.; . . Hard, N.; Okuyama, S. Clieni. Coninrim.,2000, 151.
MqNH
1 . DCI , cat DMAP AcCN , heat
\
2. BnOH
H
M:m
also genesates esters fium alcohols Macor.;Cuff, A.; Cornelius, L. T~mdlerlrorzZxrt., I Y Y Y , 40, 2733.
EtzNH
L 7 0 % BnH N
PhNO,, 3 qcr),Se F
Et2N Yang, Y.;
82%
Tctrulwdron Lett., 1999, 40,4845.
NHPh
76%
251
Punides from Esters
Section 83
5% Pd(PPh3)4, Py ,C 0
PhSNEtz
*
8O"C, 10 h PhS Hiraike, II.; Morita, M.; Tanaka, A,; Sugoh, K.; J. Org. C ~ C I IIY99, I., 64, 7305.
m;
1. BuLi, TIIF, 0°C
- rt
PhNHCOEt 2. EtC0,Et , -78°C Ooi. T.; Tayama, E.; Yamada, M.; M a r u o k a . . Y y n l e t t , 1999, 729. PhNNz
a N H
pivalic acid
+ Qo
73%
H
BtC1 , a t PdCl,(Ph&2 C O , MeCN
GW 48%
Cho, C.S.; Jinng, L.H.; Shim. S.C. Synrh. Conimitn., 1999, 2Y, 2695.
(fcl,NEtj,CO a t
95%
Sid,, THF , 1 0 min
C4Me
Ph-N-Du
90%
NEt2
PdCl,(PPh,), , 100°C MeCN, 1 d
Bu
80%
-
Cho, C . S . ; Wu, X.; Jiang, L.H.; & S.C,; Kim, H . K . J. Heterocyclic Cham., 1999, 36, 297.
SECTION 83: AMIDES FROM ESTERS
I
Ph Wang, Y.;
I
Ph
NaN(CHO), , MeCN ,6O"C
J. Org. C h e n ~21101, , 66, 3238.
Ph
Ph
86%
252
Coinpndiuin of Organic Synthetic Methods, Vol 11
Section 83
a t RhCl(PPh3h,3OoC P(OMe)3 ,toluene LiN(SO2Ca4-4-Me)
OMe
* 96%
Cvdns.;Rohinson, J.E.; Moffett, K.K. Org. Lett., 2001, 3, 3269. 4
.
&
O
2
q
o
M
, 1 h, rt M 0.5 BnNH2, MgBr,THF
e
e
:
0
q
N
m
94%
Guo.;Dowdy, E.D.; Li, W.-S.; Polniaszek, R.; DeIaney, E.
n
0
Tetmherlrnn Lctt., 2001. 42, 1843.
NII2
Ph 0
5% RhZ(tpa)d , 2 3 e q M g O , DCE 1.4 eq PhI(0Ac)z ,40"C, 12 h
K'7,
74%
Ph
ois. J, Angew. Chcni. Int. Ed., 2001, 40, 598.
Espino, C.G.; m
cat
Pd(PPh3)4 , EtOH
1 . 2 q (F'hOhP(O)N,
Ph
p,rMK""'
2 eqNi1N3 ,80"C
0
81%
Qhmoto. H.; Nishihara, S.; Yainamoto, S.; IIino, 11.; Nozawa, A.; Suzuki, A. Synlett, 2000, 991.
1. BkSO2Me ,NEt,
PhCOOIl
* PhCONHt-Bu
ggX75%
2. t-BuNIIZ
Bt = henmtliazyl He, H.-Y.; Suzuki, K. J. Orb. Cheni., 2000, 65, 8210.
95% U
O
E
t
L a a 3 7H20 0 EtOIT2 reflux, 5h H U;Bai, Y.; Wang, Z.; Yang, B.; Ma, H. Tetruhedrnn Lett., 2000, 41, 9075.
Section 84
A n d e s from Ethers
Bn 90% Tetrahedron Lett., 2000, 41, 10273.
Chang, M.-Y.; Chang, B.-R.; Tai, H-M.;
P hCOzMe
253
-
PhNII, , mimowaves, t-BuOII
1 inin
PhCONI IP h 83%
Varina. K.S.; Naicker, K.P. Tetrulwdron Lett., 1999,40, 6177.
1. BnNHTs , LRMDS
?
Bn( Ts)N
B n(Ts)N /
2. Rh(PPh3hC1, THF P(0Meh , 3 0 T
c3H7
(3 : 1) 84% Kohinson, J.E.; Nelson, J.D. J. Anr. Chcnz. Sor., 1999, 121,.6761.
SECTION 84:
AMIDES FROM ETHERS, EPOXIDES AND THIOETHERS
Ph-N=CkO,
3% I’d(I’Ph,),
Ph
TIIF, rt Larksarp, C.; Alper. 11. J. Org. Cherrr., 1999,64, 4152.
1 . p-TolS02NH2 ,dioxane KzCO3 ,catTEBA
57% 0
c:613134 2. TsCI , Py , DCM N-TS 3. KzCO,, MeCN Alhanese. D.; I-andini, D.; Penso, M.; Petricci, S. Ittruhedron, 1999, 55, 6387.
c6H1”o
91%
Section 85
Compendium of Organic Synthetic Methods, Vol 11
254
SECTION 85: AMIDES FROM HALIDES AND SULFONATES HZNCHO , DMAP , 120°C 10% PdClZ(PPh3h , 18 h * F3C@ dioxaie , autoclave , 5 har CO Schnyder, A.; Beller, M.; Mehltretter, G.; Nsenda, T.; Studer, M.; J . Org. Clierri., 2001, 66, 4311. NHzN€IBoc. 1% CUI 10% 1.10-phenanthroline
C S ~ C ODMF ~ , ,80T Wolter, M.; Klapars, A,; B u c h w' u Org. k t t . . 2001, 3, 3x03.
YBoc
\
N €12
97%
TBSO-%
TBso \,&'QC) N
C
e
B
! /
r
H
PdZ(hda), , xantphos ,3.5h Cs&03 ,dioxane , 105°C*
"0 \ /
Yin, J.; Ph-C I I=NP h
OTf
*
0
95%
BzNIIl, 1.4 CSZCO~,16 h5 xmtphos/cat Pd2(dha)3 dic~xilne,100°C
t - B u O N H f 3 z
\ /
94%
Org. Lett., 2000, 2, 1101. BnBr,BNAH,hv,4h
*
c
Nc+P
Browning, R.G.; Mahmud, H.; Badarinarayana, V.; Lpvelv. C.J. Tetruliedron Lc.tt., 2001, 42, 7155. t -B
NH,
71%
w.A.F,
Ph-N
*
Ph-I
\ 1
Ph
87%
/ph
VN+fi
BNAH = 1-henzyl- 1,4-dihydronicatinaniide Jin, M.; Zhang, D.; Ynng. L.; I-ium. Y.; Tetrulierlron Lett., 2000, 41, 7357. p-TsNII,, KzC03
I O*Et
Bunce.; Allison, J.C. Synth.
*
DMF Cnnrrrrrtn., 1999, 29, 2175.
62%
'rs
COZEt
Section 87
255
Anides from Ketones
SECTION 86: AMIDES FROM HYDRIDES
dN(
NIICOzEt
M
L
n
W
88%
, ddv. . J&; Suhha Reddy, B.V.; Kumar, G.M.; Madan, C . Synlett, 2001, 1781. TBDM S Q.
TBDMSQ
%
Cat RuOz, N d O 4
I B oc
COzMe
aq EtOAc
*A N
0
C0,Me
I
>95%
Boc Schmitt, A.C.; Jiang, W . Tetruliedron Lett., 2001, 42, 5335.
;-
PhI(OAc), , T s N H ~
PhA
!luorinatud Mn porphyrin
NIWs
- A Ph
X 1% (S8% conversion) Yu, X.-Q.; Huang, J . 4 ; Zhou, X.-G.; Che. C.-& Org. Ixtt., 2000, 2, 2233.
0
2% Ru-umine minplex
PhI=NTs
90% (57% conversion) Au, S.-M.; Iiuang, 1.-S.; Che. C.-hd; Yu, W.-Y. J. Org. Cliern., 2000, 65, 7858.
SECTION 87: AMIDES FROM KETONES /Ts
TsNIiz ,0.5 T i Q , 2 erl NEt3
P 1P h1'
-
DCE, reflux , 5 h
Ram.;Khan, A.A. Syrtth. Conwiitn., 2001. 31, 841.
83% Ph
Compendium of Organic Synthetic Methods, Vol 11
256
IIzN
K
WTS ""K""
,PhSOzNa*HZO
NH,
70%
~
HCOOH ,rt , 6 d
e 0
u; Wright, D.M.J. Aust. J. Chcnz., 2000, 53,73.
-
S
B n N 3 , TiCh , DCM 0°C
Section 87
t
rt
88%
Desai, P.; Schildknegt, K.; Agrios, K.A.; Mossman, C.; Milligan, G.L.; ,&hLL J. Ant. Cheni. Soc., 2000, 122, 7226.
1. LiCHzNMeBoc ,-7XT 2. MeOTf, -78°C 3 . satd NaHCO, , -78°C + i t 4. TFA , CHZClz 5.1SS-160"C
53x75%
J. 01-8.Ch.enz..1999, 64, 4042.
Zhang, S.;
OMvIe
.; Kouden. J,; I,asne, M.-C. Teti-ulterlron Lett., 2000. 41, 9997. EtzN
N OSOZEt
A
I'h Anilkumar, K.;
Ph
BIi3.OF,t,, DC'M , 2S"C, 6 h
1
Ph Tctrr~hr~droii Ixtt., 2000, 41, 5427
N HPh
98%
Compendium of Organic Synthetic Methods, Vol 11
262
Section 90
TFA , toluene , 110°C Me Me Cordero.;Pisaneschi, F.; Goti, A.; Ollivier, J.; Salnun, J.; Brandi. A. J. Ant. Clierri. Soc., 2000, 122, 8077. Me
BuLi , -78°C
BocN( L i t S O 2Ph Demhech, P.; Seconi, G.; R&&JL
+
0°C
Ts
N-
N-Ts
Me
BuNHBoc
t
71%
Chem. Ew. J., 2000, 6, 1281.
Zn , ALOH
t
0
92%
B 11 Bn Merino. P.; Anoro, S.;Merchan, F.; Tkjero, T. Heterocycles, 2000, 53, 861.
T s / N W
C4Et
PhCH=C=O , toluene, 5 h
(99: 1 cis:?rans) 10% chiral amine , Proton Sponge -78°C- 25°C Ph Taggi, A.E.; Hafez, A.M.; Wack, H.; Young, B.; Drury 111, W.J.; &&J J. Am. Cliem. Soc., 2000, 122, 7831. B o q O , poly~i~ethylhydrosaoxane PhCII=N-011
PhCHlNH Boc Pd-C, EtOH , heat ChdndrdsLkhar.; , . ,, Reddy, M.V.; Chandraiah, L. Synlett, 2000, 1351.
CO2Me i-Pr
/
In , A@, AcOH THF
*
%
i-Pr
N -OH IIai-rison, J.R.; Moody, C.J.; Pitts, M.R. Synlctt, 2000, 1601.
85%
COzMe
NHAc
BiC1, , 8 min 90% iniuowaves N HPh Ph Ph Thakur, A.J.; Boruah, A.; Prajapati, D.; Sandhu. J.S. Synth. Contmltn., 2000, 30, 2105.
85%
Section 90A
Protection of Ainidcs
263
* A
1 . TEAPC , MeCN-TEAP , rt , 1 h 2 . 5 eqTsCl, 25°C , 10 h
"'"\p" Ph
"g
TEAPC = (Et,N), peroxydicartlonate
86% Feroci. M.; biesi. A,; Mucciante, V.; Rossi, L. Tetruherlron Lett., I Y Y Y , 40, 6059.
-
SiOz , microwaves, 140°C
PhCl I=NOI I
hupy.
Ph
PhCONH2
>
quant
1 inin
A; Rkgnier, S . Tctruh~cironLett., 1999, 40, 6221.
Ph
1. PMeq. PMe,, TIIF, 12 2. Bn02CUl, rt
N3
97%
Ph
tZT1Zd.;IJrpi, F.;
Tetruhedmn Lctt., I Y Y 9 , 40, 7.515.
M?SiCl, A q O , heat, 10inin PhN3 Barua, A.; Bez, G.; w a . N.C., Synlctt, I Y Y 9 , 553.
PhNHAc
90%
CF3 1. BuMgCl , cat CkCN-2 LiCl HMPA-THF , 3 0 min 2. II3O+ 3 . P h C K l , NEt,
F,C Tsutsui, 11.; Ichikawa, T.;
SECTION 90A:
BocHN,
S
,
t
Bull. Clie~n.Soc. Jpn., I Y Y Y , 72, 1869
PROTECTION OF AMIDES
BnBr ,Bu3P 1,1'-(~odicai.honyl)ipiperidine
S
0 2
Winum, .I.-Y.; Barragan, V.; w r o .
,Rda
Bn BocN,I
02
J.-L. Tetruherlron Lett., 2001, 42, 601.
86%
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 7 PREPARATION OF AMINES
SECTION 91: AMINES FROM ALKYNES
GH13
-
PhNH2, PCy3 , toluene
*
1
79%
l.S%[Rh(cod)J BF, C6H13 Hartung, C.G.; Tillack, A.; Trauthwein, 14.; Beller. M. J. Org. Clzein., 2001, 66, 6339.
f-(
100 psi NH3
OMe
100"C,14h
82%
N Hetrde. V.B,; Renga. J.M.; Owen, J.M.Tetrahedron Lett., 2001, 42, 1847.
Et
=
Et
Et
1. PhNII2,3% Cp2TiMe2, toluene inicmwaves , 3 h
N I-IW
2.H2,5~PPd/C,THF,2S°C,3d * 54%
Bytschkov, I.; Dove. S , Eur. J . Org. Clz~in.,2001, 4411.
Ph
Z
Ph
1. Ph2CHN2 , 3 % CpzTiMq , 110°C 2.112 , P d C , THF, 25°C , 3 d PhJ
Ha& E.; Sieheneicher, H.; Dove. S. Org. Lett., 2000, 2, 1935. P h = P h
PhNH2 , 1 % Cp2TiMe2 C,D, , 90°C
Ph Haak, E.; Bytschkov, I.; Dove. S. Angew. C l i m . Int. Ed., 1999, 3S, 3389.
67%
Ph
52%
Section 94
Amines from Aldehydes
265
SECTION 92: AMINES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 93: AMINES FROM ALCOHOLS AND THIOLS
PhNCO
o\
*
69%
N NHF'h Huang, T.-B.; Voronkov, M.V. J. Org. Chem., 2002, 66, 1043.
;-
1. (EtO)2P(0)NHC0,t-Bu1D U D TPP , TIIF,It , 2 h
B uOI I
*
76%
BuNII3' OTS-
2. TsOII , 1120 , EtOH , refhx Klepacz, A.; Z w i w u Synth. Contiiriin.,2002, 31, 16x3. 1. NH,CO,Ph ,' P A
Laurent, M.;
*
2. IiOH , MLCN , H 2 0 , 50"C, 3h
01I s
PhCI120H
.Gph
80~95%
NH2
Synrlwsis, 2 0 0 0 , 667.
-
1. NaN3 ,CCId-DMF
e
Ph--NHz
95%
2. > 2 PPh3 IWdy, G.V&; Rao, G.V.; Subramanyam, R.V.K.; Synth. Comnzun., 2 0 0 0 , 30, 2233.
SECTION 94: AMINES FROM ALDEHYDES
CHO
Bn
1 . p-anisdine , I X M , MS 4A 2. TMSI, BuLi , TIIF
-78°C-
*
It
NBn2
PMP =p-niethoxyphenyl Reetz, M.T.; Lee. W.K, Org. Lett., 2001, 3, 3119.
Bn (4
1) 88%
Section 94
Coinpendium of Organic Synthetic Methods, Vol 11
266
OH
Cl
K2CO3, 1 h cuso4 Sharehi.;Sarvari, M.H. Synlett, 2001, 9 9 . piperidine, PhSiH3
1) quant
(0 (1
0 ) quant
Ma*ND
THF 0.02,Brtu,~16S h! S ~ C ~
70%
Xiao, W. Org. Lett., 2001, 3, 1745.
R-;.
BuCHO, Et2Zn ,toluene 10% dipeptide m i n e H2N
10% Z ~ ( O ~ - P ~ ) , = I I O ~ -Bu P~
OMe
H
69% (97% ee)
OMe
Porter, J.R.; Traverse, J.F.; Eovevda. A.11.: Snapner, M.L. J. Am. Chern. Soc., 2001, 123, 10409. I12NCH2C02Et, 2eq NaOEt EtOH , M@4
,reflux, 4 h
Meziane, M.A.A.; Royer, S.; Bazureau. J.P. Tctruhedron Lett., 2001, 42, 1017.
PhCH0,HNMe2 5MLiC104/ether
.a .l . dl.; S Azizi, N.; Nairni-.Tarnal, M.R. TetruAerfrorr Zxtt., 2001, 42, 8111.
70%
Section 94
267
Amiiies from Aldehydes
-
0 . 2 q T i c 4 , Et2NSiHMe, , 3 6 h
PhCHO
CH,CI2, 0°C rt Miura, K.; Ootsuka, K.; Suda, S.; Nishikori, H.; PhCHO
PhCHzNEtz
t
-
‘
1. T i ( 0 i - F ~ MezNH, )~~ MeOH ,rt 2. NaBHj , rt Synrh. Cnmniun., 2000, 30, 2001.
90%
Synlett, 2001, 1617. PhCI12NMe2
ClH*H2N
Y=
NHyCo
*
Hz , 2 0 %Pd(OIl)z/C EtON ,rt
Y
93%
WY.; Sercel, A.D.; Johnson, D.R.; Colhry, N.L.; Sun, K.-L.; Roth, B.D. Tetmhedron Lttt., 2000, 41, 8225. PhCIIO
polymethylhydrosiloxane-Ti(Oi-Pr)4
-
M BnpH
90%
B nNH2 , TH F , 5 h Chandrasekhar. S.; Keddy, Ch.R.; Ahmed, M. Synlett, 2000, 1655. ~ C I - 1 0
*
toluene, ntflux NII2 6M HC1 Matsupi.;Tahussa, F.; Minamikawa, 1.-i. Tetruhedl-on Lett., 2000, 41, 8523.
PhCIIO
IJ2’O ,TIIF , 0°C
*
IIZN Suwa, T.; Sugiyama, E.; Shihata, I.; Baha. A Synthesis, 2000, 789. BuNIIz, NiC126 IIzO/MeOI-I
Me
+ ph= )lc= -J
BuzSnCIH--IIMPA, 1 h
* P hCIi2NHBu NaBH, ,rt Saxena, I.; Borah, R.; Sarma. J.C. J. Cherii. Soc., Perkin l’runs. I , 2000, 503. PhCHO
61%
99%
80%
268
Section 96
Compendium of Organic Synthetic Methods, Vol 11
BnONHz , BEt, , DCM ,20°C
P hCHO
BF,*OEt,, MgSO,, 1 d
Miyahe, H.; Yarnakawa, K.; Yoshioka, N.; fiaito.
CHO
NHOBn
t
AEt
Ph
83%
T.Tetruheciron, 1999, 55, 11209.
1. MqN-SiMe, , LiClO,/ether 2. MqPhSiCl , it
Naimi-Jamal, M.R.; Mojtahedi, M.M.; Ipaktschi, .I.; J. Chem. Soc., Perkin Truns. 1, 1999, 3709. Related Methods: Section 102 (Amines from Ketones)
SECTION 95:
AMINES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 96: AMINES FROM AMIDES
5
AlCi,, PhH
0
w u p a w a . Y.; Aoki, Y.;Sakamoto, T. .I. Org. Chein., 2001, 66, 8612.
1. MeLi , DME, -78°C 2. TMSOTf ,-78°C 3. t-BuLi , ether, -20°C
-+
25°C
Ahn, Y.; Cardenas, G.I.; Yang, J.; Rolno. D. Org. Lett., 2001, 3, 7511.
58%
Section 96
Amines fmrn Anides
269
1% R ~ ( C O ) ,,,5 % Et,Nrr 96%
toluene , lOO"C, 16 h 3.5 eq HSiEt3 Igarashi, M.; Fuchikami. T. Tetruhedron Lett., 2001, 42, 1945.
Q
1. MqSiCl
II
0
2. PhMgBr
90%
Ph
Coindet, C.; Comel, A.; Kirsch. G. Tetruherlron L.ett., 2001, 42, 6101. PhNIISOZ(2-pyl-idyl)
10 q Mg , MLOII , 0°C
+
PhNH,
86%
3h Pak.; Litn, D.S.Synrlz. Cnnimun., 2001, 31, 2209.
Li, Z.;
a M
-s,rar
0
It
YmF N
H
, 5 min
95%
Tetrulzerlron Lett., 2001, 42, 8507.
Bubnov.;I'astukhov,
F.V.; Yampolsky, I.V.; Ignatenko, A.V Eur. .I Org. . Chcwi., 2000, 1503.
1. t-BuLi, ether, -78°C 2. LiAII-14,ether, reflux *
Jones.; Storey, J.M.D. .I. Clwni. Snc., Prrkin Truns. I , 2000, 769. , aq NaOH , 80°C mcl +
(CH,=CHCH,),N
56%
NH Z 40 h H 2N SdLhmVdld.; ,. . . Winsor, D.L.; Mnskos, K.; GI-imm, C.; Ilarned, 0.;Vigo, T.L.; Bertoniere, N.R. J . Org. Cheni., 2000, 65, 9234.
210
Coinpendiuin of Organic Synthetic Methods, Vol 11
a H N
Section 9 6
l.B(C€I2CI-I=CH2)3,TIIF, 65°C , 2 h 2. Mt0I-l 90%
3.qNaOII
&ov. Y u . ~ Klimnkina, ; E.V.; Zhun, I.V.; Pastukhov, F.V.; Yampolsky, I.V. Pure Appl. Chmi., 2000, 72, 1641. Ph/\""h
TMSCl , N d , MtCN
Phf i N O f i I 88% I b2Ph heat, 3-4 h H Sahitha. G.; Reddy, B.V.S.; Abraham, S.; Yadav, J.S. Tetrukeclron Lett., 1999,40,1569.
I
2.1
9-BBN, TIIF
C - B n
t
6 N - B .
96%
reflux, 1 h
Collins, C.J.; Lanz, M.; Singaram. B. Tc,truheclron Lett., Z999,40, 3673.
01'13s
b N\
1. Na naphthalenide , DME , -78°C 2. HzO
-
Ts S.C.; Seth, P.P. Tetruhcclron Lett., Z999,40,61x1.
-.
O G
N\
89%
H
LiI13B*NMe2,THF, 65"C, 2 h t
86%
&-Bn Flaniken, J.M.; Collins, C.J.; I.anz, MM.; Sinearam. B. Org. Left., Z999,1, 799 BII3OTHF , THF, heat 0a
N
I
0
* cI )
Tr Akula, M.R.; Xahalka. G.W. Org. Prep. Proceed. Int., 1999,31,214. Related Methods: Section 1OSA (Protection of Amines)
N
Tr
81%
Section 97
h n i n e s from &nines
27 1
cN-p
SECTION 97: AMINES FROM AMINES PhCl , 3
t-BuOK
*
92%
Beller. M,;Breindl, C.; Riernieier, T.H.; Tillack, A. J. Org. Chent., 2001, 66, 1403. Ph
PhB(OH), , H 2 0 , r t , O2 cat [Cu(OI-I)(t~nedu)]~Cl~ overnight J.P.; Zhong, M.; Zeng, L.; Costanzo, S. J. Org. Ch.eriz.,2001, 66, 528. 1 . r-BuLi , ether ,-78°C
s
~
30 min
M 2. PhCH2Br ~ ~
Q-Ph i2e2
99% Itiuni, K.; Kame, T.; Mitsudo, K.; Nokami, T.; Yoshida. J.-i. J. Org. Chmn., 2001, 66, 3970.
1. L i , DTBB I'h a-"-
* a N P
2. HZO
Yus. M.: Soler, T.; Fouhelo. F. .I. Org. Cliern., 2001, 66, 6207.
K
N-PMP
Pd(OzCCF3),, R-BINAP , rt
& F7 C
C02Et
100 atin 112 , CF7CI120H , 1 d
Ahe, H.; m.€I... IJnev. & . Org. L,ett., 2001, 3, 313. NHBn+ B F456p;:DCM,it
(c
h
>99%
H
& F,,C
>99% (88% ee ,R )
2% CpRu(SS-Chiraphos)II
/
/
Magee, M.P.; Norton. .I.& J. Am. C ~ W JSnr., L 2001, 123, 1778.
/
/
90% (60% ee)
212
Compendium of Organic Synthetic Methods, Vol 11
--Q
Ph
10%peptidic ligand 10%Zr(0i-Pr),
0Me
Section 97
Et :
Ph
Et,Zn, i-pIOIJ toluene
I
84% (93% ee)
Porter, J.R.; Traverse, J.F.; J. Am. Chem. SOC., 2001, 123, 984.
2.5%PCy3,6O0
THF ,20h .ran, K.L.;
70%
; Ellman, J.A. J. Am. Clicm. Soc. 2001, 123, 2685.
Li I THF ,-20°C , 4 h 2. 1. ri,o
-
"
O
A
r
n
>9J %
AzzLnd.; . . Pilo, L.; Piras, E. Tetruherlroiz Lett., 2001, 42, 129.
b;
b
& H
1% CuCl, 10% chiral diamine 2.1 K3PO4, 110°C , Id dioxane
' J. Ani. Chern. SOC.,2001, 123, 7121. Klapars, A.; Antilla, J.C.; Huang, X.; Buchwald. S.L,
pyirolidine , EtOII , wflux 2% flr(cod)Cl]z, 8% P(OPhh 3h Ph
(96
Takeuchl.; IJe, N.; Tanahe, K.; Yarnashita, K.; Shiga. N. J. Am. Cherii. Sor., 2001, 123, 9525.
:
4) 95%
Amines from Atnines
Section 97
PhOTf Pd(OAc), , dppf
X
N
273
Q
n
h
DABCO, DMSO 80°C
KuJ..; Marcoux, J.-F.; Davies, I.W.; Reider, P.J. Tetruhedron Left., 2001, 42,
, NIIB z
JL
NHN I IBz
sic13
DMF, 0°C , 18 h
Ph
159.
*
ph+ 79% (1:99 syn:unfi) Hirahayashi, R.; Ogawa, C.; Sugiura, M.; Kobayashi, S . J. Am. Chem. Soc., 2001, 123, 9493.
EtI , InC13 , Mn2(CO),,
A
Bn
r-r Et Friestad, G.K.; Qin, J. J. Am.
A
/
se
hv
s,
Et
Et
Clieiii.
Snc., 2001, 123, 9922.
o 0 y q
MeMgBr, toluene, rt
.
~
cat Sc(OTf)3,3 h
P I1 Saito, S.; Hatanaka, K.; Ph
90%
Synlett, 2001, 1859
C
N-CCIK)
*
Ph Iwasaki, I:.; Onomura, 0.;Mishhna, K.; Kanernatsu, T.; Maki, T.; Tetrulierlrnn Lett., 2001, 42, 2525.
Ph Biscoe, M.R.; Fry. A.J. Tetrulirdron Ixtt.. 2001, 42, 2159.
)lr
Ph
Ck$iH, CH2CI,
Ph
79%
274
Compendium of Organic Synthetic Methods, Vol 11
cNa
Section 97
a t Ru,(CO),~,CO , 21 h
CII,=€H,, i-&OH , 140°C Et
92% (54:46)
Chatani, N.; Asaumi, T.; Yorimitsu, S.; Ikeda, T.; Kakiuchi, F.; J . Am. Chern. Snc., 2001, 123, 10935.
Kim, Y.K.;
1
)use. L;Bercaw, J.W. Tetruhedron Lctt., 2001, 42, 2933.
NHi-Pr
1. hv (254 tun)
Likhotvorik, I.T.; Tippmann, E.; Ela
.S. Tetruhedron Lett., 2001, 42, 3049. 1. EtMgBr ,THF ,-78°C
E0,C
/
Niwa, Y.; 'lakayaina, K.; Shunizu. PhNtI,
* p-An-NHEt
2. air, aq KOH , EtOII
M.Tetruhedron Lett., 2001, 42, 5473.
1. ZnEtz , Cu(acac), , EM-hexane
+
i PhNIIEt 2. 10% MCl (9 : 3.10% aq NaON Brides, C.; [Iarnett, J.J.; Doris. E. Tetruhetlron Lett., 2001, 42, 8301.
Chrzanowsk;r.; SokoIowska, 1. Tctruhetlron
91~84%
PhNEt,
1) 95%
77% (32% el?) Asyiniii.,
2001, 12, 1435.
Me
Amines froin Amines
Section 97
PhBr ,cat Pdz(dba)3, DINAP NaOt-Bu , toluene , 80°C , 1 d Tetruheclron, 2001, 57, 2953.
Cai, W.;
(IIOCH2CH2)3N*€ICl, 20 h cat R~€lz(PPh3)4, 180°C SnC12*2HZO , aq dioxane
N Hz Kim, J.II.; Kim, T.-J.;
;-
275
a *
P h I I N q 53%
85%
H
Tetrulzerlron, 2001, 57, 3321
BnCI , CsFXelite , MeCN PF1zNBn 70% Ph2N€I IIayat, S.;Rahman, A.-u.; Choudhary, M.I.; Khan, K.M.; Schumann, W.; paver. E. Tetruheclron, 2001, 57, 9951.
N-OB n
2.5 i-pr
98% (68% ee) Fontalne.;Namane, C.; Meneyrol, .I.; Geslin, M.; Serva, L.; Roussey, E.; Tissandib, S.; Maftouh, M.; Roger, P. Tetruheclron Asyriirii., 2001, 12, 2185.
c
Ph
o
d/N\
,LBF~,MLCN t
ph 88% (85:15 trurnscis) Yadav. J.S.; Reddy, B.V.S.; Madhuri, C.R.; Sahitha, G . Synthesis, 2001, 1065.
€1.
L
Q
b
B
r
1
Pdz(dba)vdppf
NaOt-Bu ,dioxane , 110°C , 6 h
Cheng, J.; Trudell. M.I, Org. Zxtt., 2001, 3, 1371.
66%
Section 91
Compendium of Organic Synthetic Methods, Vol 11
276
PhNII,
-
PhB(OH), , 2,6-lutidine, air
5% Cu(OAck, 10% myiistic acid Antilla, J.C.; Buchwald. S .L. Org. Lett., 200Z, 3, 2017. B'\
A
SmBr,-HMPA, rt
*
Br,
PhNAPh
19%
NII
AMe
>99%
Ph 15 inin Ph Knettle, B.W.; Flowers II, R.A. Orb'. Letr., 2001, 3, 2321. cat L,LnEL(TMS), C'&6,12S°C, 9 h
>95% Org. Lxtt., 2001, 3, 3091.
..
CI 12=C€ICH,ZnBr TIIF, 0°C
-+
rt
Ph
I1 van der Sluis, M.; Dalmolen, .I.; de Lange, B.; Kaptein, 13.; Org. Lett., 2001, 3, 3943.
9
. P.L; Soldevilla,
PhlNH
+ PhI
A,; Sampedro, D.; m u e z .
; Broxterman, Q.B.
Or& Lett., 200Z, 3 , 4087.
10% Cu(neocup)(PPh3)Br
78%
P h,N -Ph t-BuOK , toluene, 110°C , 6 h Gujadhur, R.K.; Bates, C.G.; Venkataraman, D. Org. ZXtt., 2001, 3, 4315. 2. EtI
i-PiO,C
3. aq NI14Cl
-ep'
Cqi-Pr
cozi-pr1. Na , NI13 I-Pr0,C
b h o e . T.J,; McRiner, A.J.; Helliwell, M.; Sheldrake, P. J . Chcm. Soc., Perkin Trans. 1, 2001, 1435.
Et
H
98%
277
Anincs from Anlines
Section 97
PhII , 5 eq NC13, rt , 1 h
NH2
N I IMe
Me r Ohwada, A.; Nara, S.; Sakmoto. T.; J. Chem. SOC.,Perkin Truns. 1, 2001, 3064.
92% .
chiral Zr catalyst, toluene
Ph
013
Gastner, T.; Ishitani, H ; Akiyama, R.; K&ay&LL ' m
B
*
74%(55% ee) Angew. Cheni. Int. Ed., 2001, 40, 1896.
, Yh, I'MSCI
r
l'hvN-Ph TIIF
* R
Synrh. Cotnniitrz., 2001, 3 I , 273.
Su, W.; Li, .I.;
2.5 eq
P hCH= N-P h
Y 7 N HPh
5
%
In , N€IdCl, EtOII
t PhCI12NIIPh icflux, 10 h Banik.; Hackfeld, L.; Becker, F.F. Synth. Contrnun., 2001, 31, 1581.
m
B
r
, SlllIZ
THF, 6 h,O"C
.+
- k NIIPh
P hCH=N-P h rt
a
Ph kim.; IIan, K.; Park, K.J.; Bai, K.H.; Jun, Y.M.; Baik, W. Synth. Comnirtn., 2001, 31, 2297.
00
decalmrane , rt , 3 0 inin 37% IICIIO in MLGI-I
91%
I
tI
Jung, Y.J.; Boe, J.W.; Yoon, C.-O.M.; Yoo, B.W.; yoon. C.M, Synth Contnrun., 2001, 31, 3417. PhNH,
Bu,NBr, cat Ru,(CO),, , dioxane SnC12-2 IIzO , 180°C , 2 0 h
Cho. C.S,; Kim, J.S.; Kim, 1I.S.; Kim, T.-.I.;
95%
t
PhNHBu
Me
(+5%PhNBuz)
68% Syntlz. Conitnun., 2001, 31, 3791.
278
Compendium of Organic Synthetic Methods, Vol 11
N-Ph
A
2 q EtMgCl, THF ,20"C 10%Cp2ZrC1, , 15 h
Ph Gandon, V.; Bertus, P.;
Xh
*
78%
Ph
Eur. J. Org. Cheni., 2001, 3677.
*
II2
, fermcenyl-hinaphthyl complex of I r 40 h
Ph
NHPh
- A Ph
quant (84% ee)
Angew. Chein. Int. Ed., 2001, 40, 3425.
Xiao, D.;
-
Et3NI-I' IICO2-, IICOOI1
PhCH=NP h
Section 97
PhCH,NHPh microwaves, 4 inin Mophaddam.; Khakshoor, 0.;Ghaffarzadeh, M. J. Cheni. Res. (S), 2001, 525.
PhA "
Y
1. &Br
)(
l u
, D M Fl ,hr t
*
N
2. AcOEt , 1N HC1
€I
OH
95% (>99% de)
OH
Yanada.; Kaieda, A.; Takemoto, Y. J. Org. Cheni., 2001, 66, 7516. BnNI-I,
2.5 eq PhCIIO , 4 eq HCOOII
w
micmwaves, 5 inin
B nBHB n 59% (+ 40% Bn3N)
Torchy, S.; Barlvy. D. J . Clwn. Res. (S), 2001, 202.
li(i-Prl3 eSi(i-Pr)3
H
$3 P -
SnC14 , toluene 0°C. MS 4A
O2N
Ncivama.; Suzuki, M.; Kagoshima,
OZN
l11111ll11
#
91%(84:16cis:trms)
13. Heterocycles, 2000, 52, 529.
Section 97
Amines from h n i n e s
N -C,
H7
ITIF, r t , 4 h
279
*
&
Denisenko, A.; Denisenko, S.N.; Arend, M. J. Heteroryclir Cherii., 2000, 37, 1309.
;-
C A N , aq MeCN, rt B n,N -C7I I, + BnNII-C,II, 69% Bull, S.D.; Davies. S.G.; Fenton, G.; Mulvaney, A.W.; Prasad, R.S.; Smith, A.D. J. Chem. Soc., Perkin Truns. I , 2000, 3765.
& AcO.
B uNI 12
Ph
I OAc
-t B uNI1Ph Cu(0Ac)Z , THF, S O T , 14 h I'edorov, A.Yu.; Finet. J.-P. J. Cherii. Soc., Perkin Trans. 1, 2000, 3775. .
MS 4 A ,DMF ,23"C 77% 28 h Salvatore, R.N.; Schmidt, S.E.; Shin, S.I.; Nagle, AS.; Worrell, J.H.; J,lrg, K.W. Tetruhedron Lett., 2000, 41,9705.
N I IBn 'I'MSN3, MLCN O
N
-
B
n
rt , 2 5 h
Chandrasekhar, M.; Sekar, G.; &@, V.K. Tetrulieciron Lett., 2000, 41, 10079.
Xekou Koulotakis, N.P.; I-Iadjiantoniou-Maroulis, C.P.; Tetruhedrori Lztt., 2000, 41, 10209.
64%
66%
280
Compendium of Organic Synthetic Methods, Vol 11
oy
Section 97
-d\” &
N-Ph
[PhSiH, , Ti catalyst, MeOII ,pyiulidine] i-BuNH2 , slow ddition , 60°C
63% (99%ee)
’
IIansen, M.C.; J j u c h w u Org. k t t . . 2000, 2 , 713.
PhI, Pd2(dhah ,THF , 1 d cszc03 biphenyl amino-phosphine
*
PhH N H2N Edmondson, S.D.; Mastracchio, A.; Partnee, E.R. Org. Lett., 2000, 2, 1109. 1 . PhCMO ,Ti(Oi-Pr), 2. vacuum
B t12NH
/
mBr
7
68%
3. ,TIIF,In B n2N Choucair, B.; L h n , 11.; Mir6, M.-A.; Lehreton, C.; Mosset. P, Org. Lett., 2000, 2, 1851.
,,&‘
DDQ , DCM , HzO , ~tt-
,&”
B n2N
BnHN
86%
Hungerhoff, B.; Samanta, S.S.;Roels, 1.; Metz. P, Synlett, 2000, 77.
0”) & H
/
*
80%
Yadav. JS,; Reddy, B.V.S.; Rasheed, M.A.; Kurnar, H.M.S. Synliqt, 2000, 487.
1. ChTi(TADD0L) + BINOL , 6 h 2 a 1 M q S i C N , CH2C12,-40°C mpN13n
2. € 1 2 0
*
NI 1Bn p>
CN
95% conversion 31% ee) Byrne, J.J.; Chavarot, M.; Chavant, P.-Y.; VallCe. Y. Tetralledron Lett., 2000, 41, 873.
Section 97
Amines from Amines
Ph21+BF4-, 10% CuI 2 eq Na,CO,, DCM , rt , 6 h
28 1
-
C N - F ' h
65%
S . - L ; Lee, S.-H.; Ixe,D. Synlett, 2000, 1022.
30% aq H 2 0 2 , acetone
Ph
ph*
0.1% Mn,O(OAc),(TPTN) Bull, S.D.;Davles.;Fenton, G.; Mulvaney, A.W.; Prasad, R.S.; Smith, A.D. Chern. Conirrictn., 2000, 337. 5 % Cp2ZrClz , 'IHF , 6 h 2 q BuMgCl ,22"C
de Armas, .I.Kolis, ; S.P.; Hovevda. A . K J.
hi.
Chern. Soc., 2000, 122, 5977.
1.2.2 eq t-BuLi ,-78°C pentane-ellier 2. (-)-sparkine
*
3. -4O"C, 1.5 h 69% (93:7 er)
Bailey. W.F.; Mealy, M.J. J. Arir. Cltetii. Soc., 2000, 122, 6787. 1. t-BuLi , (-)-sparkine toluene,-90"C ~
\Bn
2. H,O+
\
Bn
85% (87% ee) Gil, G.S.; Groth, LJ.M. J .
h i .
Cherri. Soc., 2000, 122, 6789.
MtCN nicotinilun , Ivflux, dichroimte 1.5 min
H
*Etozc)p COzEt
E t O 2 C m C O 2 E t
Mohaiiunadpoor-Baltol-k, I.: Memarian, I1.R.; Suhhani, S. Synth. Corizniun., 2000, 30, 1661.
;-'-
1
97%
282
Section 97
Coinpendium of Organic Synthetic Methods, Vol 11
p - B r , toluene
2.1 NaOt-B u cat Pdz(dha)3 , 80°C a t aryl phosphine 84%
Etozn J. Org. Chein., 2000, 65, 5327.
Harris, M.C.;
COZEt
H
Mg(HSO,), ,
D C M , r t , 10min
75%
.zolficol. M .A,; Eany-Borazjani, M.; Sadeghi, M.M.; Moha~iunadpoor-Baltork,I.; Memarian, H.R. Synth. Conrniun., 2000, 30, 3919. NaII2P03 , HCHO
; .
C3H7
C3H7
X=CN X = C0,Me Davis.;Durden, D.A. Synth. Cornnilin., 2000, 30, 3353.
*
Bu,N HSO, , (MeO),sO, toluene, q NaOH
N
Ph
chiral his-oxazoline ligand
I
X
Me
90% 83%
pJNHM 98%
NOz
Voskresensky, S.; Mnkosza. M. Syntli. Cominiin., 2000, 30, 3523. 2 eq MeLi , toluene, -75°C
N
-
--
NH-p-Tol Ph 97% (73% ee)
Denmark.;
Stiff, C.M. J. Org. Chen~.,2000, 65, 5875.
Oxone, 8O"C, SiOz , 8 h B u ~ 1.N1 Fields, J.D.; fiopp. P.J. J. Org. Chern., 2000, 65, 5937.
b
Bu~N-OH
98%
Section 97
Amines from Amines
1.
283
-
-a-b
,36"C, 3 h
-)3*
2. aq NaOH €1 H Buhnov. Y.N.; Zhun, I.V.; Klimkina, E.V.; Igantenko, A.V.; Starkova, Z.A. Eur. J. Org. Chern., 2000, 3323. , Pd(OAch, 80°C
-\.
* PhHN PPh3 , Tr(Oi-Pr)4, MS 4,& ySne S.-C7,; Yu, C.-L.; Tsai, Y.-C. Tetruhcdron Lett., 2000, 41, 7097. PhNIl,
t
p . 1 1 2
Ph(0i-Pr Ac),
98%
88%
i-Pr
-
Saito, S.; Kano,T.; Ohyabu, Y.; Yamamoto. H. Synlett., 2000, 1676.
Coldham.I.;Fernhndez, J.-C.; Snowden, D.J. Tetruhedron Lcctt., 1999, 40, 1-propanol , 300°C
80%
1819.
* PhCII2NIIC3H7
*O0/O conversion 77% monoalkylation 5% dialkylation Valot, F.; Fache, F.; Jacquot, R.; Spagnol, M.; Lemaire. M . Tetruhedron Lett., 1999, 40, 3689. PhCHzNHl
y-A 12O3
[lie(CN).jNO]-', MeCN
BuNH~
*
BuZNH
N2 . - Tripani, C. Tctruherlron Lett., Doctorovlch.; Z999, 40, 4635.
'"\=
S i n , I2 , rt , 3 0 nun
N -1'h
some inines gave diiners
Danik.;Zegrocka, 0.;Banik, I.; Hackfeld, L.; Tetruherlr-on Lett., 1999, 40,673 1 .
t
LNH 58% ~
Ph
Section 97
Compendium of Organic Synthetic Methods, Vol 11
284
JfBn
W S i M e 3
c
69%
5
(&3H5PdClh, TBAF, 31 h Ph Ph hexane/THF. 8 h Nakamura, K.; Nakamura, H.: yamamoto. Y. J. Org. Cherlt., ZY99, 64, 2614.
Et
H Amedondo, V.M.; Tian, S.; Md&n&l. . Ph
F.E.. M,lrks.T, . . I J. Am. Chem. Soc., 1999, 121, 3633. 4
4
.
CHiCl2, 40°C , 2 0 h PhJMe ..Kainz, S.; Brinlanann, A,; W r . W.: P f
Ph
-
0.15%1chiral Ir catalyst, H2
N I IBz
xMe
88%
99.7% (83%ee ,R )
Ph u J. Am. Chcni. Soc., Z999, 121, 6421. NHBz
Sic13
96% D M F , r t , 1h
Ph Ph KohavJ,,hl.; .. Hirahayashi, R. J. Am. Chctri. Soc., 1999, 121, 6940.
C5H 11N1l 2
Ph3SiH (Ph2CIl)PhN-Yh(hmpa)4
t
C5H NHSiPh3
61%
. . Kamata, T.; Miura, Y.; Shishido, T.; Takehira, K. J. Org. Chem., 1999, 64, 3891. nakakl.;
Xh
Ph ;-
* P h fiPh N
TiCh ,NEt,
I
90%
Ftl
Srinivas, G.; Bharathi, P. J. 01-8.Cl?em., 29Y9, 64, 4204.
N / Ph
-SiMe3
,5 h
1% D A F , THF, MS 4A
-
93% ph
PhA H Wang, D.-K.; Zhou, Y.-G.;Tang, Y.; &>u. X.-L; Dai, I..-X. J . Org. Chem., Z999, 64, 4233.
Section 97
Amines from Amines
285
1 . Pd(OAc), , r x BINAP , 8 W C NaOt-B u tolUtXlle
2 . Pd(OAc), ,NaOt-Bu, 80°C:
chirlll phosphine toluene
Harris, M.C.; Geis, 0.; Bn, Bn-011
-Ph
1
d d . S L J. Org. Chern., 1999, 64, 6019.
.
TsCl , Py , DMAP
--
k
DCM,rt, 12h
!Jundrasekhar. S.;Mohanty, P.K.; Narikishan, K.; Sasmal, P.K. Org. Lett., 1999, I , 877.
NIIMe
MeIIN
W(C0), , COII2IKzCO3
E M
McCusker, J.E.; Grasso, C.A.; Main, A.D.; WC1wee-W
*
MeNu 48%
erg. h t . , 1999, I , 961.
Tortolani. D .R.;Poss, M A . Orx. L ~ t t . I,Y Y Y , I, 1261.
Nv
I Roesch, K.R.;
PhCXPh, Na2C03,8 h .5% Pd( O A C ),~LiCl DMI' , 100°C Orb'. La., l Y Y 9 , I, 1551.
85%
Compendium of Organic Synthetic Methods, Vol 11
286
1. DDQ , PhH, MS 4,4 L-
2. 0.1N HCl Sampson, P.B.; Bonek. J.F, Org. Lett., 1999, I, 1395. TMSN3, acetone
a
NHCH2Ar
% ,
BuBr , CsOH*H20, 21 h 'Iiz
DMF ,MS 4 A ,23°C
Salvatore, R.N.; Nagle, A S . ; Schmidt, S.E.;
1.5
,AcOH
&GeB3
Ph*N-h
71%
C,H7NH3 C1
5% Crcornplex Ar = 2,4dinitrophenyl Li, Z.; FernSndez, M.; Ja01-6' Iktt., . ZYYY, 1, 1611. ph-
-
+
60"C, 1 h
Ph2C€INHGII,
Section 97
-
Ph-
N3
quant (70% ee)
NHBu
Org. Zxtt., 1999, I, 1893.
*
0.5 BF3eOEt2, MeCN ,0°C Ph Akivama, T.; Iwai, J.; Onuma, Y.; Kagoshima, H. Chcni. Conimun., 1999, 2191.
89% ~-
90%
t
cat MgIr ,TIIF
(91 Alper, P.B.; Meyers, C.; Lerchner, A.; Siegel, D.R.; Carreira. E . N Angcw. Chmi. Int. Ed., 1999, 38, 3186.
Locher, C.; Peerzada, N. J. Clzein. Soc., Perkin Truns. I, I Y Y Y , 179.
1) 55%
92~87~70%
Section 97
Axnines from Amines
287
ZnCI2, microwaves Montmoiillonite K10
143"C,35 min
4 d s k L L ;GuihB-Jampel, E.; Petit,
GO%
A.; Loupy, A. Synth. Coniniun., ZYYY, 2Y, 1 3 4 9 .
2 eq E a r , DMSO , K2C03
PhNI-I,
PhNBt,
It , 6 h
95%
P.M& ; Bhaduri, A.P. Synth. Cnnrniun., 1999, 2Y, 2085.
Srivastava, S.K.; -.
B nBr , K2CO2-Al2O3
N
miaowaves, 5 min
>c) I N
I1
98%
Bn Jasiinghani, H.G.; Khadilkar. B.M. Synth. Contnricn., ZYYY, 2Y, 3603. - -(Si (Me)
;-
.
, . >
I-I-O--)n-
ZnC1, , ether Reddy, M.V.; Chandraiah, L. Synth.
.
Ph,NAPh H Coiirriiun, I Y Y Y , 29,- 3981.
67%
:
cNl>\
Brimhle. M . A . ; Gorsuch, S. Aust. J . Chern., I Y Y Y , 52, 065.
H
[Rh]/BiPhePhos , PhII H2/CY) ,XO"C, 20 h cat
(CH2)y
Bergmann, D.J.; Campi, E.M.; Jackson. W.R.; Patti, A.F. Aust. J. Chenz., 2999, 52, 1131.
C7II 1s CP7
MeHN
1. NCS , toluene ,it , 3 0 min 2. Bu,SnH , AIBN , toluene reflux , 1 h 3.10%)XI KF
Senhoku.;Ilasegawa, €I.; Orito, K.;
D
* Bu
I
59% Me Hetcmcycles, ZYYY, SO, 333.
"#I,#,,
c+,5
Compendium of Organic Synthetic Methods, Vol 11
288
Section 98
REVIEWS : "Amines Via Nucleophilic 1, 2-Addition To Ketimines. Construction Of Nitrogen-Substituted Quaternary Carbon Atoms," StelniL. A.G.: SDero. D .M, Org. Prep. Proceed.. Int., 2000, 32, 205. "Catalytic Enantioselective Addition To Imines," Kohayashi, Sh.; Ishitani, H. Chem. Rev., 1999, 99, 1069.
SECTION 98: AMINES FROM ESTERS 1. LiH,BNMe2, T I I F , 25°C Ph
OMS
--
2.3M I-ICI ,MeOH
Ph
NMez
92% Org. Lett., 2001, 3 , 3915.
Thomas, S.; IIuynh, T.; Enriquez-Rios, V.;
phwPh Phw (C,HT)ZNH, 5% RU atlilyst
I I
I I
t
CHZCI2,20"C , 10 h
OC0,Et
N(C3H7)L 89% (74% ee>
Matsushima, Y.; Onitsuka, K.; Kondo, T.; Mitsudo, T.-a.; J. h i . Cheni. SOC., 2001, 12, 10405. OAc
I
4
Ph
Ph
NIIB n
cat Pdz(dba)3 ,BnNH,
I
S-BINAP, THF, 2 d
Ph
79% (39% ee ,Sx)
Kodama. H.; Taiji, T.; Ohta.; Furukawa, I. Synlert, 2001, 385. CdI,,NIITs, rt
cat TiC14 , 5 h
Ph,>-.
*
CQI,aHN
Ph
Ph
Mahrwald.; Quint, S . Tetruherlron Lett., 2001, 42, 1655.
41%
(C3H7)2NH1 HZO ,25"C cat [l'd(C3H~)C1]2, 20 h OAc
t
tetnphosphine ligand Feuerstein, M.; Laurenti, D.; Doucet. 11... Smte . IliM,Tetruhcdron Lxtt., 2001, 42, 2313.
Amines from Halides
Section 100
289
AMINES FROM ETHERS, EPOXIDES AND THIOETHERS
SECTION 99:
NO ADDITIONAL EXAMPLES
SECTION 100: AMINES FROM HALIDES AND SULFONATES Et2NH , Pd(OAc)?, phosphine ligand
*
Ph- -I
NaOf-Bu , toluene , X0"C J. Or#. Cllerrt., 2001, 66, 2560.
Ah, M.H.; Duchwald.
b /
Ph--NEG Ph,
PhNHMe , 1.5
85%
,Me
NaOt-BU
1% Pd(OAc),, toluene, 80°C polymer- bound phosphine ligaid * 93%
t-Bu
Parrish, C.A.; D u c h w d . 5
J . O r g . C ~ C I I2001, I . , 66, 7820.
t-Bu
Grasa. G.A.; Viciu, M.S.; Huang, .I. Nolan. ; 5*,PL J. Org. Chcni.,2001, 66, 7129.
Ph-Br
1. TMS,NLi , 2% Pd(dha), , Pt-B u3
*
r t , 16h 2. IIC1 Lee, S . ; Jorgensen, M.; m w i e . J.F, Org. . M I . , 20191,3, 2729.
Ph-NH2
98%
92%
Compendium of Organic Synthetic Methods, Vol 11
290
Section 100
1. Ph3SiNH2, toluene .5%Pdz(dbah , 1.3 LiIIMDS
* 6
1.2% =l+PI( 2. H30+
e
c?
piperkline, TI-IF NaI Vt- AnONa
+
10% Ni(0)hipy reflux, 15 min
c1
x0YN-""'
p
0
: (75 Desmarets, C.; Schneider, R.; Fort. Y,Tetruhedron LL,tt., 200Z, 42, 247.
e- , cohabxime , MeOII
Et,NOTs , NaOH, rt Bu 0
Inokuchi.;Kawafuchi, H. Synlctt,
M 98%
pcY3
Huang, X.; Buchwald. S.L. Org. Lett., 2001, 3, 3417.
Bu 0
0
25) 68%
NHOMe
61% (5.6:l)
2001, 421.
Lane.;Zewge, D.; Houpis, I.N.; Volante, R.P. Tetrahedron Lxtt., 200Z, 42, 3251. pyirolicline , NaII , t-BuOH , 3 h PhCl
2V0 Ni(acac>,
*
P h - 0
8% dihydmiindazoline carbene ligand
Gradel, B.; Brenner, E.; Schneider, R.; Fort. Y . Tetruhcdron Lett, 2001, 42, 5689.
96%
Section 100
29 1
Arnines from Halides
pyrrolidine , K 2 C 4 DMSO, ultrasound 15 min
92%
Magdolen, P.; MeEiarovi, M.; US. Tctruhedron, 2001, 57, 4781.
Pd(OAch, BINAP, 18 h
c1 KzCO3, toluene, reflux
Junckers, T.H.M.; Maes, B.U.W.; LemiBre, G.L.F.; r)oinmisse. R. Tctruheciron, 2001, 57, 1021.
L m
NIIB oc
B~
-
, cat CuBr-SMq
DMF , -10°C
H
NHBoc
rt , 14 h
= 51% Hunter, C.; Jackson. R.F.W.; Rami, H.K. J. C h f m Snc., Perkin Truns I , 2001, 1349.
a-
Br , toluene, 3
11 t
cat PdC12 , hisphosphine ligand NaOt-Bu ,80"C
/
97%
%hang, X.-X.; IIarris, M.C.; Sadighi, KJ.P.; Buchwald, S.L. Cun. J. Chent., 2001, 79, 1799. OMe PhNHMe, 0.5%Pdz(clha)3 L-
15%
BINAP, NaOt-Bu ,8O"C tuluene , 29 h Wolfe, J.P.; Buchwnld. S.1,. J. Orx. Clwn., 2000, 65, 1144.
2.5%Pd2(dha)3 , indole toluene, t-BuONa , 100°C biphenyl amino-phosphine 90% Old, 11.W.; IIaiTis, M.C.; Buchwald. S.L. Or-g. Lett., 2000, 2, 1403
292
Compendium of Organic Synthetic Methods, Vol 11
Section 100
A
\p
HN
N
C
O
\ /
C
I
A
,catNi(II)/C
dppf , LiOt-Bu , toluene BuLi ,2.5 h tz. B.H.; Ueda, H. Angew. Chcm. Int. Ed., 2000, 39, 4492.
1. NUN,, MeCN 2. PPh,
PhCH,Br
3. PhCIIO
-
88%
P hCH,N=C HPh
95 %
Van&, P.; Klbn, P. Synth. Comiiiun., 2000, 30, 1503
CI-I0 l w i c N20,, microwaves
. wa . l.; Id Sapra, P.; Dave, B. Synrlt.
mpB
Conintun., 2000, 30, 4479.
DMF PPh3,,10% 110°C Pd(OAc), , 2h *
60%
51%
Kwong, F.Y.; Lai, C.W.; Tian, Y.; Chan. K.S. Tetruhedr-on Lett., 2000, 41, 10285
DME B u ~ N HPd(dba)z, , t-B uONa , rt , 20 h
-
+NBU2
86% Stauffer, S.R.;Lee, S.; Stambuli, J.P.; I-Iauck, S.I.; &&J&JJ- Org. Lett., 2000, 2, 1423.
Suwa, T.; Sugiyama, E.; Shihata, I.; 3 a h a . A. Synlett, 2000, 556. PhNIIMe , t-BuOK dioxane , Pd2(dba)3 Ar'
n Arcl-
N@N-
Ar = 2,G-di-t-Bu-C,H3 Huang, 1.; Grisa, G.; I\lolan. S.P. Org. Zn.tt., I Y Y Y , 1, 1307.
Section 100
p%n
A~ninesfrom IIalides
d3 n
IIN
6 %J
293
-
, NaOt-Bu, 105°C
\ /
, 2% €'d(dha)2
p p$Q PBr '
P(C-C6H11)2 Bei, X.; Gurmn. A S . ; Turner, H.W.; Weinherg, W.H. Tctruhtvlmn Iktt., 19YY, 40, 1237.
NII,
.Br
, toluene, XO"C, 30 I n i l l
Pd(OAc)2,
92%
PPh2
PPllz
Guari, Y.; van Es, D.S.; Keek, J N . N . ; Kamer, P.C.J.;yjul Leeuven. P.W.N.M. letruhedr-on Lm., I99Y, 40, 3789.
jf.l
P ( ~ - T O I,)2eq ~ NaOt-Bu 2% P d ( d t ~ ) dioxane ~, 3
c9
n
IIN
Br
0
6 2) 76%
(10 : Beletskava. I.P.; Bessmertnykh, A.G.; Guilard. R . Tetruhedr-on Lett., ZY9Y, 40, 6393.
Tripathy, S.; I,e Blanc, K.;J h r s t . T . Or-g. Ixtt., 1999, I, 1973.
294
Compendium of Organic Synthetic Methods, Vol 11
PhNHMe , f-BuONa , rt
-
1% Pd(OAc),, toluene, 19 h G 4% t-B~zP(2-Pb-C6€14)
N
Section 101
W
e
P 98%
Wolfe, J.P.; Quchwald. S .L. Angew. Cheni. lnt. Ed., 1999, 38, 2413.
SECTION 101: AMINES FROM HYDRIDES
0
HCHO ,BtOZCCII~NHz*llCl 10% Y (OTf), , aq TI-IF
*
N
I
30"C, 4 h
& N H C H ~ ~ ~ E ~ N
I
81%
COzEt COzEt Zhang, C.; Dong, .I.; Cheng, T.; LLB,Tetruherlrnn Lett., 200Z, 42, 461. NHPh PhNH, ,'Il3AF*3 H20 KMnO, , DMF rt,Ih
I
75%'
NO2 I Tetruhedron L d t . , 200Z, 42, 3439.
mo"
Huertas, I.; Gallardo, I.;
PhCHO , piperidine ,5 tnin
/
/
inicmwaves
70% Sharifi, A.; Miizaei, M.;
Mnnut. Chenr., 2001, 132, 875. NIIZOII , KOI-I, EtOII ZIlClZ
BaMte, J.M.; Svensen, H.; Trevisan, R. J. Chcwi. Snc., Per-kin Truns. I, 200Z, 376.
Section 102
Amines from Ketones
TBAF.3
NO2
1120,
295
PhNlI2
NIIPh
hv , DMF, rt , 3 h
NO2
Juertas, I.; Galludo, I.; w e t . J. Tttruhedron Lett., 2000, 41, 279.
54%
1% BINAP, 12 h 90%
Hicks, F.A.;
Ph
L
Org. Lett., 2000, 2, 219.
ph
y
MtONIiz, MLOII,NaOMe 4h
Ph%ph
0
0
Seko. S.; Miyake, K. Synth. Coriznim., ZYYY, 29, 2487
83%
-2: dPh
SECTION 102: AMINES FROM KETONES
1 . t-BuSONH2, Ti(OEt), 2. MeMgBr
3. IICl/MeOII
N
N Shaw. A.W.; de Solms, S.J.Tetruuliedron Lctr., 20lll, 42, 7173.
quant (60:40 -:+)
1 . Ph2NNH2, PhH , MS 4 , 4 , 6 h 2. TFAA , 0°C , 3 h
3. heat, 3 h Miyata, 0.;Kimura, Y.; &to.
'I'L Synthesis, 2001, 1635.
1
Ph
81%
296
Section 102
Compendium of Organic Synthetic Methods, Vol 11
0
1 , Me2N O
N
% >
DMSO , KF/AI2O3 2. Me1 Moskalev, N.;
-
/
'Me0
MeZN
-
60%
Chenr. Coninrun., 2001, 1248.
PhNI-12 , Montmoiillonite KSF
I
10 h
Ph
0
Samajdar, S.; Becker, F.F.;
Heterocycles,2001, 55, 1019.
96%
Kotsuki. H.; Mehta, B.K.; Yanigisawa, K. Synlott, 2001, 1323.
N I IT01
Tol-NII2, BloHl, , MeOII, 1 h
*
\I\
97%
Bae, J.W.; Ixe, S.11.; Cho. Y.J.; Yoon. C.M. J. Cltctn. Soc., Perkin Truns. I, 2000, 145. BnNII, , microwaves 30 sec
,
0
.
Tetruhedron L.ztt.. 1999, 40, 3957.
90%
l.O.l%Pd(OAc)Z,1.4 NaOt-Bu
"11, PhA
I
Bn
0.1%)Xantphos , toluene , XOC
h
2. cyclohexanone , EtOII TsOII*OM, , ieflux
N
H
Wagaw, S.; Yang, B.H.; Buchwald. S.1,. J. Am. Cfiern.Soc., 1999, 121, 10251.
92%
Section 103
Amines from Nitriles
297
1. N€IdCl, Ti(0i-Pr), , EtOII , NEt3 83% It, 10 h Ph 2 . NaBH, ,rt , 7 h .,., . BhdttdLhdTVVd.; Neidigh, K.A.;Avery, M A . ; Williamson, J.S. Synleit, ZYYY, 1781.
Ph
CI0,Et N€I2NHMe*I-ICl, EtOII 0
4
0 CCll E
n:fl ux
t
+
+
E t o 2 C c N
I
N’
I
Me
Me
1) 70%
(3
Martins. M A P . ; Freitag, K.A.; da Rosa, A.;Flores, A.F.C.;Zanatta, N.; Benacorse, H.G. J. Heterocylic Clwii., 1Y9Y. 36, 217. Related Methods: Section 94 (&nines from Aldehydes)
SECTION 103: AMINES FROM NITRILES
I’hCN
IdiBHj-NMeZ, THF , 6 Y C
*
PhCHZNI12
75 %
12 h Thomas, S . ; Collins, C.J.;Chzens, J.K.; Spiciarich, D.; Goralski, C.T.; J. Org. Client., 2001, 66, 1999. S% Ni/S02 , 10 attn H,
2M NI-I,McOH, 120°C 6h Takamizawa, S.; Wakasa, N.; PhCN Tcith, M.;
M
Synlett, 2001, 1623.
Ni(R) , NaII2IO2 , TsNI-INH,
5
A m r , € 1 ~P 0 Y , ,r t Tciralwtiron Ixtt.. 2001, 42, 2723.
e
O
\ /
PhCf I- NNIITs
e
7
96%
sponge Ni , € I 2 ,28% aq NH3 EtOII ,it, S h
a ,. Cl landkd.;Nagasawa, M.; Kasuga, Y.; Sakamura, 11.; Takuiia, Y.; Iwatani, K. ,
,
l’eiruhcrlron La., I Y Y Y , 40,5885.
86%
r
Section 105
Compendiuin of Organic Synthetic Methods, Vol 11
298
1 . EtMgBr ,Ti(Oi-Pr)4, ether
phd 70% ~
2. BF3eOEt2
Ph-CN
Bertus, P.; Szvmoniak. J. CI~eitt.Continun., 2001, 1792.
SECTION 104: AMINES FROM ALKENES
A
/(>
n
ph
NH2
cat
,CO/H2
+
€INx>
[Rh+(cod)(q6-PhBPh3)7
78%
Ph
- d-
Tetruhedron Lett.. 2001, 42, 2423.
Lin, Y.-S.; El Ali, B.;
22% Ph
cat dipho.~hiiio-~yclobutene Pd complex
Ph\ -
92%
toluene, PhNH2,S h
Ph ; Yoshifuji, M.
Minami, T.; Okainoto, H.; Ikeda, S.; Tandca, R.; Angew. Clieiti. Int. Ed., 2001, 40, 4501.
v
Ph
piperidine ,cat BuLi ,TIE
-78°C
6
It
* I
Tetrulzedron, 2000, 35,5157.
IIartung, C.G.; Breindl, C.; 'I'illack, A.;
moEt
Et2NI1, CO/H2 [Rh(cod)C1]2
Rische, T.; Bsrfacker, L.;
SECTION 105: Ph,P=O
*
91%
-Et Et2NO 75%
Eiir. J. Org. Cheni., I Y Y Y , 653.
AMINES FROM MISCELLANEOUS COMPOUNDS 1. MLOTf, DME, r t , 2 h
Ph,P 2. I.iAlI14, 0°C , 3 h h u n p t o . T.; Kikuchi, S.4.; Miura, T.; Wada, Y. Org. Lett., 2001, 3 , 87.
97%
Section 105
Ainiiies from Misc.
HC02NH4, IO%Pd-C
299
-c
NH-HCI MeOH,rt, 14h Zacharie. B.; Moreau, N.; Dockendorff, C. J. Orb. Chenz., 2001, 66, 5264.
NHz
95%
1. acetophenone, PhN 2. Bu3SnH, AIBN , PhH , 80°C
*
A
86%
Ph
Jdm&dJL; Plotkin, M.A.; Viswanathan, R.; Prahhakaran, E.N. Orb. Lett., 2001, 3, 1009.
.
95% 1101.
Hsiao.;Rivera, R.; Yasudn, N.; Hughes, D.L.; Reider, P.J. Orb. Left., 2001, 3,
Ph3SnH, AIBN, FhH
*
Crich. D.; Ranganathan, K.; Huang, X. Org. Lett., 2001, 3, 1917 /ph
Ph€IC=N
+
/0 -
Boruah, M.;
1. AlCh.6 HzO , I([,
MCN
*
2. NazS203, H 2 0 , I t
PhHC=N /ph
Synlett, 2001, 795.
UN3
2 eq PMe, , toluene, 10 eq Me1 CHZClz, 25°C , 1.5 h
Kato, H.; Ohmori, K.;
’
85%
Synlett, 2001, 1007.
90%
Section 105
Coinpendiuin of Organic Synthetic Methods, Vol 11
300
1. Meo-%
0 ~
2. NaOH , HzO2 Ph& 3. MeLi 4. NHzOSO3H Hoffmann.;Hiilzer, B.; Knopff, 0. #rg. Lc.tf., 2001, 3, 1945.
(t-BuO),C=O , 10%Pd-C , 3 h
PhNHNHZ
Z-
EtOH , 3 PHMS Chandrasekhar. S,; Reddy, Ch.R.; Rao, R.J. Synlert, 2001, lS61.
st a u 3 PI1
&
N
~
BuLi , THF, -78°C
high % ee
85%
PhNHBoc
-AI1111111111
46% (9870 ee) + 13% of 2 other isomers Pearson. W.H.; Stevens, E.P.; Aponick, A. Tetrulzcdron Latt., 2001, 42, 7361.
N -OH PhzSiH2, 1% RuC12(PPh3)
-- HZ
AgOTf, DME , rt , 2 S h 62% (83% ee)
Takei, I.; Nishihayashi, Y.; Ishii, Y.; Mizobe, Y.; Chent. Conitiiun., 2001, 2360.
2.5 BF,.OEtz , 0, MS 4 A ,CD,CN, 1 h
OH . . a m i z u . M.; Makino, H. Tctruhedron k t t . , 2001, 42, 8865.
Section 105
Fh\L-~
301
Amines from Misc.
~ , S i n , 1%r
e
A
Ph,
,OH
+
85%
DMF,H,O,lSh
Ph I1 Laskw, D.D.;
Ph Sandhu, J.S. Tetruheclron Lett., 2001, 42, 7883.
m > e Melo. T.M.V.S I q e s , C.S.J.; Cardoso, A.L.; Gonsalves, A.M.d’A.R. Tetruheclron. 2001, 57, 6203. *s;
4 eq In, IICl , aq THF ,30rnin -- PhNH2 84% I’ hNO, Lee, J.G.; Choi, K.I.; Koh, 1I.Y.; Kim, Y.; King, Y.; Cho. Y.S. Synthesis, 2001, 81.
c +
N-0
-
CN
LiCl , NaBII, , TIII:, 0°C It
*
Ram, S.R.; Chary, K.P.; k r a r . D.5 Synth. Cottinrim., 2000, 30,351 1. *&
-
98%
ZiCl, , NaBII, , ‘I’HF P hCI-I, N, PhCH,NI-I, 95% Chary, K.P.; Rain. S.R.; Salhuddin, S . ; m r . D.S, Syrith. Com/nun., 2000, 30, 3559. NaBH,. LiCl ,TIIF
P hCI I, N, Ram, S.R.; Chary, K.P.; .-
C
l
\ U/N
* PhCH,NII, 0 ° C . rt D.S. Synth. Conrrriun., 2000, 30, 4495.
FeSO4.7 HZO, NH, , rt
,
MeOH, 2.5 h
KJmdl.; , , Laxman, E.; hriludtlin, M. Totruhedron k t t . , 2000,41, 7743. Ph,+
O, N
II
;-
95%
- r I n B r
Ph,
I
N
98%
,ON
* 90% DMF,IIZO rt,3 h Anjaneyulu, S.; Reddy, E.J.; Yadav, J.S. Tetruliedi-on Lttt., 2000, 41, 9311.
A. II Ph
302
Compendium of Organic Synthetic Methods, Vol 11
N-OII
NH2 OH
NH2
of:
I-I2
cat 48%
/
Section 105
HBr
/
/
(23 1) 94% I.W*; Taylor, M.; Marcoux, J.-F.; Matty, L.; Wu, .I.; Hughes, D.; Reider, P.J. Tetruhedron Ixtt., 2000, 41, 8021.
PhCX2N3
aPhCHzNH2 NrrBI14, aq T H F , I S T , 30 min Bosch, 1.; Costa, A.M.; Martin, M.; F.: V 1 Org. Lett., 20110, 2, 397.
In, 4 NHdCI, MeOH
CN GN -
heat,4h Yadav. J.S.; Reddy, B.V.S.; Reddy, M.M. Tetruh~clronk t t . , 21100, 41, 2663. cat
a
,s.
0
NMRq Me e
i
PPh,, H2O/PhMf 5% TBN3 Wang, Y.; Espenson, J.H. Org. L.ett., 2000, 2, 3525.
p
NaBH4, C ~ C 1 2 4H
2 0
y
2
97%
Ph 1120, 10inin Ph Ringuelli, F.; Plzzo.; Vaccaro, L. Synthesis, 2000, 646. FtCl3-Zn , EtOH ,rt , 4 h
Pathak, D.; Laskar, D.D.; Prajapati, D.; NH2NMe2, FtCl,*6 H20
I
.-
PhNH,
98% Cknr. Lett., 21100, 816.
-
PhCH=N-NMez MeCN , reflux, 8 h Barrett, I.C.; Langille, J.D.; Ken, M A . J. Org. Chern., 2000, 65, 6268.
PhCH2N3
93%
quant
t
PhN,
97%
quant
Section 105
Amines from Misc.
303
+a $
1. 2 q €Ig(ClO,h*3 € 1 2 0 ,TIIF 2. NaBII4, NaOH ,M a 1 1
31%
Pearson. W [I.; Ilutta, D.A.; Fang, W.-K. J. Org. Chem., 2UUU, 65, 8326.
-
SnCl4, CHzClz Et,Si€I , 5.3 ,h0°C
Nl
B
G
N
H
M
e
91%
Lopez. F.J.; Nitzan, D. Tetruherlron Lett., ZY99, 40,2071.
-
drn dTY::;
In , NH4Cl, EtOII ,wflux, 1 h PhCHlNII, PhCH2Ny Reddv. G.V.; Rao, G.V.; Iyencar, D.S. Tetruherlron Ixtt., 1999, 40,3937.
Bu3S1iH,mm
-
I1
98%
82%
NIC:
RdlnLr.;Kennedy, .
1
I’hN3
A.R.; Chase, E. letruliedron Lxtt., ZYYY, 40,6 3 2 5 .
EtMgBr ,ether, 30min
*
PhNIlEt 90% &mar. H M .S.; Reddy, B.V.S.; Anjaneyulu. S.; Yadav, J.S. Tetruhedron Lxtt., 1999, 40, 8305.
mBr , DMF ,211
PhN,
>
82%
it , 40inin Kumar. I I .M.S.; Anjaneyulu, S.;Reddy, B.V.S.; Yadav, J.S. Syrrlett, 1999, 551.
Ph (P PD )I IN 1 . B uLi , TIIF , - 7 8 T
CN DPP
Ar
= 4-MeO-CGJI4
Ar
Ar
(60
40) 81%
KdlSLT.; . Balhi, M . Z’e~ruherlrnnAsynini., ZYYY, 10, 1001. I .
304
Section 105
Coiiipendiuin of Organic Synthetic Methods, Vol 11
MCM--silylamine-Pd(I1) complex
N 1.1,
MeOH, rt
92%
Kdntdm.; . . Chowdari, N.S.;Rahinan, S.; Choudary, B.M. Synlett, 1999,1413.
AMINES FROM NITRO COMPOUNDS FhNOz
porphyiinato-ion / NaBH4
*
PhNHz
HOCI.I,CI12Br, it Wilkinson, 11,s.; Taiioury. G.J.; Wald, S.A.; Senanavake, (7.11. Tefruhedron L.ett., 20f11, 42, 167.
95 %
M~N-BII~ pd(orr)2/c ,
* PhNHz 90% MeON, r t , 6 h Couturier.; Tucker, 1.L;Andresen, B.M.; Dub&, P.; Brenek, S.J.;Negri, J.T. Tetruhedrcin L.ett., 2001, 42, 2285. PhNOz
N,tI,*M2*H20 , A 1 2 0 3 , FtCh.6 €120
c PhNH2 inicmwaves, 5+2 inin , 108°C Vass, A.; Dudbs, J.; ’I’Gth, J.; Vnnnn. R.S.Tetruherllnn Lett., 2001, 42, 5347.
PhNOz
57% In, 9 0 , c , 4 h
KumAr, 1.S.D.;Ho, M.M.;
‘
89%
* =+-N z(I-r 85%
Tc~tr-uherlronLett., 2001, 42, 5601.
FeS-NH4C’I , aq MeOII
* PhNHz reflux, 4 h 81% Desai, D.G.; Swami, S.S.; Dabhiide, S.K.; Ghagnre, M.G. Synth. Cninrnun., 2001, 31, 1249. PhNO2
(16 Kang, K.H.; Choi, K.I.; Koh, H.Y.; Kim, Y.; Chung, B.Y.; Choi. Y.S. Synth. Continun., 2001, 31, 2277.
1) 51%
Section 105
PhNO, Yu, C.; Liu, B.;
305
Amines from M i x .
2 txj Sni , 5 % 1,511ioctyl-4,4'hipyridinium dihromide I
83%
PhNH,
M&H, rt , 3 h J . Org. Cheni.,2001, 66, 919. B,,H14 , Pd-C , a t AcOH
0 2 N - o -
C0,I I
I 1 2 N e c o , H
\ /
+
MLOI-I,reflux , 0 0 inin
97%
Bae, J.W.; Cho, Y.J.; Lee, S.11.; Yoon. C.M. Tctruh
C021I
* BrqCH2)>
selective for non-conjugated ackls Lgg, AS.-Y,; Yang, H.-C.; Su,
C0,II
mo
I:.-Y. Tetrulzerlron Lett., 2001, 42, 301.
3 eq
.MKN 4
CIIO
~XJ NEt,
L
c02Me 98%
55%
, 25°C
Coretz, G . S . ; Tennyson, R.L.; Ronio. D, J . Ant. C17ern. Soc., 2001, 123, 7945.
Vignola, N.;Dahmen, S . ; Eiders, I).; Brilse.Tetruher/r-on Lett., 2001, 42, 7833. BnBr , 5 txj K P 2 1 1 9 , 3 h
*
Ph-C02H
Ooi, T.; Sugimoto, €I.; Doda, K.;
P hCY),I I
5% BuJ'tIISO, , THF, rt . Tetmlierlrnn Lett., 2001, 42, 9245.
t-BuOH , N 2 0 3 Zn , dust, DCM
sulfur suhlinate , rt KdTmrlkrlT.; . . . Das, P.J. Synfh. Contriinrr., 2001, 31, 535.
P hCD2 N
-CO,Bn Ph
Ph02t-Bu
99%
90%
EtOI-I ,276 Fe(SO4h.x H20
> I'hCO2Et 97% GI~II~SO, Xu, Q.-h.; Liu, W.-y.; Chen, B.-h.; Ma. Y.-x. Syntlz. Cornriiun., 2001, 31, 2113.
1. MeOII, 6S"C, H 2 0 , 1 h
P hCW2I-I
microwaves
+ PhCO2Me 84% 2. I-12S04 Zhane. z; Zhou, L.; Zhang, M.; Wu, II.; Chen, 2. Syntli. Coninittn., 2001, 31, 2435.
Q-c'." ;-
. . .
MsCl , Py , O T , 40min
>Q
Begum, F.; Begum, S . Tc,truhcdron Lett., 2001, 42, 9059.
C02Me
71%
312
Coinpendiuin of Organic Synthetic Methods, Vol 11
: -
toluene, 100°C
-
Section 107
3
97%
cat [Ru[ PhCII=C(Ph)CnCPh)(PMei-Pr2 }]
JimCnez-Tenorio, M.; Puerta, M.C.; Valerea. P,; Moreno-Dorado, F.J.; Guerra, F.M.; Massanet, G.M. Chern. Corninun., 2001, 2324.
coZH
@
COzMe
KOI:i:Y:O.MeI
Br Br ,4vila-Zirraea. J.G.; Mariinez, K.Synfh. Coniinun., 2001, 31, 2177.
-
BuOH , NdlSOd*IIlO
BtCO,€I
94%
EtC02Bu
&
96%
x f l u x , 3 0 inin Li. Y.-0. Synrlr. Cor~iiiiun.,I Y Y Y , 2Y, 3901. Ac20 , Zn/AlC13 , DMF
PhSSPh
; -
... ,
.
PhSAc 65°C. 4 h Fadaei, Z. J. C h m . Res. (S), 2001, 22. I
.
80%
COT1I
CXHI7OH -coZcSH M%N*HCI ,NEt, ,0°C * Ph MLCN, 3 h Wakasugi, K.; Nakamura, A,; w w .Y, Te.trulie(IronLL'tt., 2001, 42, 7421. Ph
w Ph
C
0
2
H
CXH ,,OH , toluene , 80°C , 4 h diphenyllrinmonium tiifh te
*
Ph-
17
93%
c02c&17
93% Wakasugi, K.; Misaki, T.; Yainada, K.; Tanahe. Y. Tetrulledron Lett. 2000, 41, 5249. MeC02II
BnOH , act. C , miLrowaves
L, MtC0,Bn 12 sec Sapar..;Shinde, N.A.; Bandgar, B.P. Org. Prep. Procc~cd.Irit., 2000, 32, 287.
ji,,,
Ph
83%
BnSII , 4 eqP41II0,toluene llO"C, 4 h
PhSBn'
Sudalai, A.; Knnagasahapathy, S.; penicewicz. B.C. Org. k i t . 2000, 2, 3213.
96%
Section 107
Esters from Acids
9.."
313
MeOH, NaHS0,-SiO, 45 h q
96%
H
C0,II
C0,Me
cr cmzH
Das.;Venkataiah, B.; Madhusudhan, P. Synlett, 2000, 50. 1. SOCl, , Arnherlyst A21
DCM
2. MLOH
Ir
Girard. C.; Tranchant, I.; NiorE, P.-A.; Ilerscovici, J. Syrrlett, 2000, 1577. PhCH,CO,I-I
NaI-IC04-Si02, EtOAc
+
Phff-I,CO,Et
rt,6h Das.;Venkataiah, B. Syntliesis. 2000, 1671.
* Bu
Br'(collhPF6, CHzCb
95%
,yflr
60%
Bu
Homsi, F.; pousseau. G . J. Org. Chetn., 1999, 64,81. P hC0,I-I
89%
EtOH , 2 eq Py , DCM ,rt
*
95%
Pha,Et
Isohe, T.; Ishikawa, T J . Org.Chon., 1999,64,6984.
-ti.
1. LiOII , IIzO
-
I' hC0,Me 2. MqSOd A K .; Basak, A.; Grover, V. J. Org. Chent., 1999,64,8014.
PhCY),II
1
Ph
CO,II
MtOH, F~(SO,h-xH,O itflux, 3.5 h
9G%
-1
G.-S.; Gong, 11. Synth. Conirnctn., 1999, 29, 1547.
I'h
COZMe
83%
Compendium of Organic Synthetic Methods, Vol 11
314
20%F%( SO4h.x HZO ,M&II
PhCOzH
4h Synth. Conintun., 1999, 29, 607.
L.
Section 108
PhCOZMe
82%
Further examples of the reaction RC@H + R'OH --P RC02R are included in Section 108 (Esters from Alcohols and Phenols) and in Section 30A (Protection of Carhoxylic Acids).
SECTION 108: ESTERS FROM ALCOHOLS AND THIOLS
C6H13
;-
1
DEAD, PhMe ,PhCOOH polymer-hound phosphine
QBz
*
--
rt,lh c61113 Janes, M.K.; Boezio, A.A. J. Org. Chenz., 2001, 66, 2178.
83%
\ , A T&phlo Ph
Ac@ , DCM + 99% 1 % V(O)(OTf), ~ e n . C 30 min .- ; Kuo, J.-H.; Li, C.-H.; Barhate, N.B.;Hon, S.-W.; Li, T.-W.; Chao, S.-D.; Liu, C.C.; Li, Y.-C.; Chang, I.-H.; Lin. J.-S.; Liu, C.-J.; Chou, Y.-C. Org. Lett., 2001, 3, 3729. AczO, YEr based catalyst 0
-
O
4h
.
2
Kurnar.; Pandey, R.K.;
99% (also with amines) Bodas, M.S.; Dongare, M.K. Synlett, 2001, 206.
2 eq A ~ ,O cat L~QO,
25°C Ph Nakae, Y.; Kusaki, I.; Sato. T, Synlett, 2001, 1584.
IIzN
011
graphik/montmonlloriite K10 mimowaves, 8 m i n , 130°C
-
HZN Frkre, S.; ThiCry, V.; w o n . T, Tetruhedron Lett., 2001, 42, 2791.
61% 0
Esters from Alcohols
Section 108
315
AczO ,cat NBS ,C€12CI,
PhCHzOH
>
rt,4h . . Kanml.; Seradj, H. Synlett, 200Z, 519.
PhCHzOAc
94%
AgzO, TsCl , KI , 2 0 T
won
M t a-ors
*
MeO
60%
UA.;Le Berre, N.;Sauv6, G . Terruhedron Lett., 2001, 42, 8781.
[hmim]C1*2 AICI, ,3O"C
Iro
OM
EtOAc , 10 min HO ~~
Potdar, M.K.; Mohile, S.S.; Salunkhe. M.M. Tetmhedron Lett., 2001, 42, 9285.
95%
DCC , DMAP , DCM lSCPa,rt, 1 d 92%
Shlmlzu.;Hiramoto, K.; 1
.
.
Synthesis, 2001, 1027. Ti04/S04-2, MeOH
96% Ph COzH reflux, 2 h Ph &n. T.-S.; Ma, Y.-R.; Li, Y.; Sun, X . ; Li, T.-S. Synth. Conintun., 2001, 31, 2051. Pd(II)-hydrotalcite, F'y ,Oz OH
*
56%
toluene, 8O"C, 28 h
0 Kakiuchi, N.; Nishiinurn, T.; Inoue, M.; Uemura. S . Bull. Chent. Soc. Jpn., 2001, 74, 165.
PhCH,OI 1
AcOII ,BiCl, , 1 h
z
PhCI-120Ac
95%
v; Khosrupour, A.R.; Aliyan, 11. J. Chent. RES.(S), 2001, 280.
Compendium of Organic Synthetic Methods, Vol 11
316
f
i
s
2. 1 .P T BAAPFii NMO THF
Section 108
dT:
c 3H 7
(45% ee)
GH7 Leroy, B.; Dumeunier, R.; M i u k L E Tetruhedron Lett., 2000, 41,10215.
Okada.;Iwashita, S.; Koizumi, N. Tetruhedron Lett., 2000, 41,7047. 1. CCHzCN , AcOII
Et,C-OH ;-
1
.,
*
HZSO.4 + Et 3 C-N H3C I 2. thiourea, AcOIIlEtOH Kauss, V.; Kalvinsh, I.; Gold, M.R. Syntlzcsis, 2000, 1709.
Ph
pL
%;.
BuBr ,C s 2 c 0 3
OH
Chu, F.; Dueno, E.E.;
a
L
o
Tetruhedron Lctr., ZYYY, 40,1847.
2
;co)3c% M a
TBN , DMF, 93”C, 1 d
,PhH, 3 NEt3
ultiasound , 3 h
89%
/
y Bu
91%
M a
0
/ \ -
Caldwell, J.J.; IIamity, J.P.A.; Heron, N.M.; Ken-. W.J.; McKendiy, S.; Middlemiss, D. Tetruhadrnn Lttt., 1999, 40,3481.
pL OH
BnC1, Cs2C03 CO, , DMF ,TBAI ,23”C , 4h
Ph L
y
o
B
94% 0 Kim, S . 4 ; Chu, F.; Dueno, E.E.; Jung, K.W. J. Orx. Charn., ZYYY, 64,4578.
n
317
Esters from Aldehydes
Section 109
N-trifluoroacetylsucinimide
C,,I 1~,0r I
*
18 H3
7OZCcF3
95%
THF ,refhx , 5 h A .R.; Yang, B.; Qiu, G.; Zhang, Z. Synthesis, 1 Y Y 9 , 55.
-v.
1. C 0 2 , Bu3P, CyTMG , DMF
* PhCH20C02CII2Ph 2. CBr4, 2 h KddokrlWd.; . IIaliu, 11.; Fukumachi, S.; Karasu, M.; Tagaya, H.; Chiha, K. J. Chent. Soc., I'cr-kin Truns. I , I Y Y 9 , 2205. P hC3IZOI I
67%
Further examples of the reaction ROH + RCOzR' are included in Section 107 (Esters from Acid Derivatives) arid in Section 4SA (Protection of Alcohols and Phenols).
SECTION 109: ESTERS FROM ALDEHYDES
Hsu J.-L.;
m.1.-M, J. Org. Clwnl., 2001, 66, 8673.
actr0 CO$llyl
2.1.H30+ e-
*@'
Franco, D.; PuAach. E. Synlett, 2001, 806.
0
OAl(Oi-Pr)z
m
CIIO
1%
oAl(oi-pr)2
DCM , r t , 2 h Simpura, I.; H e v a w Terrulidron, 2001, 57, 9867. CI10
95%
/
-
0
A4\
Oi-Pr
0
CaO , PhlhlI ,313"K. 1Smin
Seki, T.; Ilattori. €-I. Chetn. Cnrnniun. 2001, 2510.
99%
318
Compendium of Organic Synthetic Methods, Vol 11
PhCI.10 Gopinath, R.; &&&Jj&
M ~ O H ,I , 0 2 ,cat v20,
*
Section 109
PhC02Me
quant
Org. Lert., 2000, 2, 577.
w o n . S.& ; Wan, 2.;Peelen, T.J.; Spencer, K.L. Tetruhedron Lett., 1999, 40, 6535.
a hiphenylene A1 catalyst
0
Ooi, T.; Miura, T.; Takaya, K.;
*
Tetruhedron Lett.. 1999, 40, 7695.
99%
19:1 trms:cis) 62% (>19:1 cis:frcms)
with SnCh ,-78°C Wang, Y.; Zhao, C.; Romo. D . Org. L ~ t t .Z999, , 1, 1197. cat (Sm12 + I-PrSII) *
'
r
8
8
%
Mxc3
Org. Lett., 1999, I , 1989.
C3H7C02Na, PdC12(PPh3)t ,80"C CO PhII, 18 h Cho, C.S.; Bark, D.Y.;
*
62%
/
0 J. Heterocyclic Client., 1999, 36, 289.
Section 110
PhCHO
Esters from Alkyls
3 19
1. 2% chiral hicylic amino-alcohol Et,Zn , hexluieholuene ,0°C , 3 h
-Pi1M QAc
2. A c ~ O
98% (98% ee)
Nueent. W . 4 , Cheiii. Coirzniun., 1999, 1369.
i
cHO
0
1. (pinylhB ally1 ,ether
-1OO"C, 1 h
2. p-TsOH , heat
COzMe
8 2 ~ 9 0 %(>99% ee)
Ramachandran, P.V.; Krzeminski, M.P.; Reddy, M.V.R.; Brown. 1-I.C. Tetruhedron Asyiiini., IY99, 10, 11.
1. PhCIIO
=(C02H
TI IF/H2O 2. 6M HQ
Choudhury, P.K.; f:ouhelo, F.; 1,
PhCI-I0
,In , 2 0 0 ~
p
h
v
o
t
75%
Tetruhedron, 199Y, 55, 10779. ,0.5 TaCl5, 0°C
-S /M i e3
DCM,Ih
2. A c 2 0 , r t , 12 h
70%
Ph Chandrasekhar. S.; Mohanty, P.K.; Ram, A. Syntlz. Connnttn., 1999, 2Y, 257. Related Methods: Section 117 (Esters from Ketones)
SECTION 110:
ESTERS FROM ALKYLS, METHYLENES AND ARYLS
-
No examples of the reaction R-R RC@R' or R'COzR (R,R' = allcyl, aryl, etc.) occur in the literature. For the reaction R-H + RC02R' or R'COzR, see Section 116 (Esters from Iiydrides). 1. 1 atm CO ,CBr4/2 AlBr, CHzBr2,-40°C , 2 h
2. i-I'iOH
L.; Petrovskii, P.; Vitt, S.; Orlinkov, A. Tetruhedron Lett., 2000, 41, 9903.
C02i-k 82%
Compendium of Organic Synthetic Methods, Val 11
320
Section 111
SECTION 111: ESTERS FROM AMIDES
10%MgBq ,MeOH
Ph4
lJ Jo
N
8h
Ph&OMe
Orita, A,; Nagano, Y.; Hirano, 1.;Qtera. J. Synlett, 2001, 637.
K
ph
C ~ B r ~ l L i 0 t u- B, T€IF
NI INH 2
20 min
H2N
(
H
Ot-Bu
88%
Cheni. Zxtt., 2001, 466.
OQg(CHz0H
OH C
-1 Ph
Yamapuchi. J . - i ; Aoyagi, T.; Fujikurd, R.;
/
97%
GCN N
a
*
1120 ,75"C, 16 h Yorimitsu, 11.; Wakahayashi, K.; Shinokuho, H.; Oshima. K. Bull. Chent. Sor. Jpn., 2001, 74, 1963. O -H
H20,75"C, 16 h H PL
I
HO,VN=N=CO,W
*
O
CN water soluhle radical initiator Yorimitsu, H.; Wakahayashi, K.; Shinokubo, 11.; -K.ct!-uher/ron
m
95%
O
Lett., 1999, 40, 519.
1. CAN
O
\
2
N
GNHNH2
2. MeOH, rt
Stefane, B.; KcZevar, M.; Polanc. S. Tetruhedron Lett., Z999, 40, 4429.
*
97%
Section 113
321
Esters from Esters
SECTION 112: ESTERS FROM AMINES NO ADDITIONAL EXAMPLES
SECTION 113: ESTERS FROM ESTERS Conjugate reductions and conjugate alkylations of unsaturated esters are found in Section 74 (Alkyls from Alkenes).
Evans. P A . ; Kennedy, L.J. J . Am. C h w . SOC., 2001, 123, 1234. PhBr , catPd(dba)z, rt
Or-Bu Lee, S.; Beare, N.A.;
-
PhJ
NaNTMq ,12h
Ot-Bu
J. Am. Chem. Soc., 2001, 123, 8410.
r-BuOK , ether, 0°C EtC0,Me Vasin.;Razin, V.V. Synletf, 2001, 658.
IZovle.; May, E.J. Synlert, 2001, 967.
(98 63% ee
t
EtCOzt-Bu
2)
69%
87%
71%
Compendium of Organic Synthetic Methods, Vol 11
322
Section 113
BuOH ,L a o 4
Bdndedr.; , . Sadavarte, V.S.; Uppalla, L.S. Synlett,
88%
C0,Bu
toluene, heat, 2 h
C0,Et
2001, 1338.
C,H@H, cat NBS , 100°C toluene, 3 h
C02Me
94%
m; Uppalla, L.S.; Sadavarte, V.S. Synlert, 2001, 1715. a
1
F e S 0 4 , BuOH , toluene reflux, 2 h
uOEt
also with Cu.W4 (88%) B.P.; Sadavarte, V.S.; Uppalla, L.S. Synth. Contntim., 2002, 31, 2063.
85%
C,H@H, NaBPh, , bluene
* j j C 0 2 C J I ,
reflux, 2 h
L C O z E t
90%
b d e a r . B .PG;Sadavarte, V.S.; Ilppalla, L.S. C h m . k t t . , 200Z, 894.
-
BuOH ,Zn, toluene COzBn
heat, 2 h
Bandear.;Sadavarte, V.S.;
Uppalla, L.S. J. Chenz. Res. (S), 200Z, 16.
98%
Rucatdyst , i-PIOII
'
20"C, 23 h
C0,Me Evaraere, K.; Scheffler, J.-L.; Mortreux, A.; MeMgBr ,THF , 1 h
99% (94% ee ,S ) -
0 Tetrahedron l ~ t .2001, , 42, 1899.
b P h-S02Me 77% O"C+ It Steensma.;Calahi, S.; Tagat, J.R.; McComhie, S.W. Tetrahedron Lert., 2001, 42, 2281.
PhSO2CF3
Section 113
Esters from Esters
323
cat [Ku(acen~Cl~)]~
chiral ligand , r-BuOH Z-BuOK
OBU
Or-Bu
>99% (67% ee) Everaere, K.; Mortreux, A,; Bulliard, M.; Brusse, J.; van der Gen, A.; Nowogrocki, G.; Carpentier. J.-F. Eur. J. Org. Chmt., 2001, 275.
J
Ph
TBAFO
OSiMq
€120,
BnBr
* Ph
T H F , r t , 1.5h
96%
Ooi, T.; Sugimoto, 11.; m u o k a . I(.Heterocycles, 2001, 51, 593.
. . Wl,llld . ms.;Blann, K.; IIolzupfel, C.W. Synth. Coiiiinun., 20OZ, 31, 203.
L
BuOH , Amkrlyst-15
COzMe
toluene, =flux, 2 h
*A/ COZB u
85%
Chavan.; Suhharao, Y.T.; Dantale, S.W.; Sivappa, K . Synth. Cormzun., 200Z, 31, 289.
phho
Me4Sn , 25% Pdz(d1x&, 80°C* 10% AsPh3,10% CUI , N M P , 87 h
0 possi. R.; Bellina, F.; Kaugei, E. Synlett, 2000, 1749.
oJ--)hp
58%
0
1. dilauryl peroxide , PhH , reflux 2 . 5 eq E 6 0 , N 3 , PhCl 0
Ollivier, C.; -1.
dilauryl peroxide, 100°C
P. . I . Aiii. Cheni. Soc., 2000, 122, 6496.
N3
80% (74:26 eno:endo)
Section 113
Compendium of Organic Synthetic Methods, Vol 11
324
AOTBDMS Wang, W.; Xu, M.-H.; Lei, X.-S.; Lin, G.-Q. Org. Lett., 2000, 2, 3773. 5 eq CsOAc , 0.1 DMAP
Hawryluk, N.A.; &,&r&R
HN -OH
A
c
O
m,+" Y f 85 %
t
Ns = nifrohenzenesulfonyl J. Org. Client., 2000, 65, X379.
Lipase Novozym 435 ,65"C isooctane , MS 4A
NH
I
74%
Lu, W.; sib. C.J. Tetruhedron LEtt., 1999, 40, 4965.
;.w-
Pugh, G . Tetruhedron k t t . , 1999, 40, 7595. PhC02Me
EtOH , 4 h
*
PhCO,Et 89%
Ilankumaran, P.;
e . J . G J . 01-8.Chein., 1999, 64, 3086.
Section 114
325
Esters from Ethers
Enholm.; Gallagher, M.E.; Moran, Org. I x t t . 1999, 1, 689.
K.M.; Lomhardi, J.S.; Schulte 11, J.P.
B uOH , Mo-ZiO, , toluene
* M
reflux
Reddv. B.M.; Reddy, V.R.; Manohar, B. Synth. Cornniun., 1999, 29, 1235.
O
B
98%
REVIEWS: "Stereochemistry of the Alkylntion of Idactones,"Ihrahim-Ouali, M.; Pnrrain, J.-L.; Org. P r i y . Prori~oil.Itit., 1999, 31, 467.
SECTION 114:
i i
Bu
ESTERS FROM ETHERS, EPOXIDES AND THIOETHERS Bu
2% PPNCo(CO), , 9 0 0 psi CO
*
B1~,-Of'tz,DME , 80°C, 1 d
PPN = his(tiipheny1phosphine) iminiuin Lee, J.T.; Thomas, P.J.; J . Org. Chetn., 2001, 66, 5424.
'a,
1 . M d l s , DCE , 8 O T
B uOBu
2. BzCl ,8WC Guo, Q.; Miyaji, T.; Gao, G.; IIara, R.;
t
75%
Chetn. Conirnun., 2001, 1018.
L>' u u'. l h L ; Graziano, M.L. Tetruherlron ,!,eft., 2001, 42, 93. '
PhCO,Bu
66%
u
Compendium of Organic Synthetic Methods, Vol 11
326
9
TBDMS"'"'
1. cat Pd(0Ack , cat P(OPh), TIIF
2. MeMgBr ,-78"C, 1 h
*A Me
MaZC
Section 114
g
78% (74% de)
T~DMS
Marion, F.; Le Fol, R.; Courillon, C.; Malacria. M. Synlett, 2001, 138.
BuY30H*B
Madhushaw, R.J.; Li, C.-L.; Shen, K.-H.; IIu, C.-C.; J . Am. Cheni. Soc., 2001, 123, 7427.
P b(OAc)&3(
OAc k
78%
Py , PhH, reflux
&g&,.L&;
Payen, A.; Warshakoon, N. Tetruizerlron Lett., 2001, 42, 2047. F&13-Monftnorillonite K 10
BnOBn .: Mova
* BnOAc AcZO ,70°C, 22 h Fasihi, .I. J. Chem. Soc. (S), 2001, 378.
w; .' '
7
1 . 2 eq A d l , DCM, O T , 18 h
2 . 4 NaIICD3 Tetruhedron Lett., 2000, 41, 5799.
C 0 2 ,5% NaBr ,NMP lOO"C, 30 h OZN
[ 18% with Phuxirdne]
OZN
Iwasaki, T.; Kihara, N.; h d o . T. BidZ. Clieni. Suc. Jpn., 2000, 73, 713.
94%
327
Esters from Halides
Section 115
0
NaBrC), , KI-ISO, , H 2 0 , rt
80%
0 Metsger, L.; Bittner. S. Tetruhedron, 2000, 56,1905.
-
0
M%SiONOz /C103
65%
Shahi, S.P.; Gupta, A.; Pitre, S.V.; Rcddy, M.V.K.; Kumareswaran,
J . Org. Clterii. 1999, 64,4509.
Ph
M&gnf.
Ct,BnNCl, KMnO, , DCM
OMe
reflux, 6 h
K.;Vankar. Y.
* A
J.11.; Choi, B.Y. Synth. Conmiin., 1999, 29, 2405.
Ph
OMe
85%
SECTION 115: ESTERS FROM HALIDES AND SULFONATES Br
2.3 MtC0,t-Bu 2.5 LiI-IMDS ,toluene
C02t-Bu
3% I'd(OAc)z, 1 h 6.3% bipheiiyhminophosphiiie S'.I.. .I. Ain. Cliern. Soc., 2001, 123, 7996.
0
Moradi, W.A.;
c1
/
C O , BuOII , 130"C, 15 h 0.1 PdCI,(PhCN)2, 25 h a 0.6 dppf, NEt,
*
84%
0
COZBU
95%
Beller. M.; MSgerIeiri, W.; Indolese, A.F.; Fischer, C. Synthesis, 2001, 1098.
BuWI , CO , 3 eq NaOAc , MS O.S% [PdCI,(I'hCN)7_1 , 145°C fenoce~iyldipho-Thine MPgerlein, W.; Indolese, A.F.; Deller. M.Angcw. CllelJt. Int. Ed., 2001, 40,2856. 45 atrn C 0 , A I B N hexandMeCN , 80°C
c0,IIt ~
o
l
b S nl B u 3
, 12 h
*
do
COZEt Kreimerman, S.; JXVu. I.: Minakatn, S.; Komatsu. M. Org. Lett., 2000, 2, 389.
84%
328
-
Compendium of Organic Synthetic Methods, Vol 11
* 2. H20 Sato, A,; Ito, H.; Yamaguchi, Y.;
Section 116
CO2Et
aTetruhedron Lett., 2000, 41, 10239. '
72%
Zheng, T.-C.; Burkart, M.;Pichardson. D.E. Tetruherfr-onLetr., 1999, 40, 603.
C O , PdClz[P(OEt)& OH
2.2NEt3, 130°C , 18 h 200 a t m C 0 2 (supemitical)
ncl
Kayaki, Y.; Noguchi, Y.; Iwasa, S.;
C O , EtOII , NaOAc , 135°C Pd(0Ac)z ,dppf , 1 h
Et02C
c1
Bes ..s;lrd.;Crettaz, R. Heterocycles,
-0
; Noyori, R. Clieni. Cornmun., 1999, 1235
CO2Et
99%
1999, 51, 2589.
Related Methods: Section 25 (Acid Derivatives fromHalides).
SECTION 116: ESTERS FROM HYDRIDES This section contains examples of the reaction R-H (R = alkyl, a v l , etc.).
-t
RC02R' or R'C02R
0
65% chiral hipyridine , 2 ddiol
Lee, W.-S.;
5% [C'u(MeCN)d] BF,
aOxPh
u; Chan, 11.-L.; Choi, W.-W.; Ng, L.-Y.
Tetruliedron Asyrnnt., 2001, 12, 1007.
57% (52% ee, R )
Section 116
Esters from IIydiides
0
329
1%KuCl3-n NzO, MeC0GI TFA,DCM,rt,4h
li
Ph
77% Chern. Corninun., 2001, 65.
-
Komiya, N.; Noji, S . ;
Ley
1 . TI(OTfh , DMF , 6 0 T 2. H Z 0
Ph
*
&
94%
0
h
Lee. J.C.; Jin, Y.S.; Choi. J.-11. Cheni. Conzrmn., 2001, 956.
C0,B n
13%
C02Bn
,30"C,8h
0 . 1 sc.(o,soc~,z€~~5),
*
81%
0 -
Tetrolzerll-on Lett., 2000, 41, 3107.
Mori, Y.; Kakumoto, K.; Manabe, K.; PhCO,r-Bu , 5 % C u ( 0 T h 7.5% trk(oxazo1ine) ligimd acetone, 0°C , 2 d
Ph 80% (83% ee)
Kohmura, Y.; Katsuki. T. Tetruldrnn Lert., 2000, 41, 3941.
S t Q ,A%O, 0,
J-( f
reflux, 12 h
Koltun, E.S.; Kass. S.R.Synthesis, 2000, 1366.
(I9
(84
Akhrern. I.; Orlinkov, A.; Afanas'eva, L.; Pelrovskii, P.; Vitt, S. Tetruhedron Lttc., 1999, 40, 5897.
1)
36%
16) 98% ee)
Me
Me
$
II
eo
Mihovilovic, M.D.; Chen, G.; Wang, S.; Kyte, B.; Rochon, F.; J. Org. Cheni., 2001, 66, 733. 1 '31(3,S-di-CF3-GH3S e h _
2 q 60%)H 2 0 2 , CF3CHzOH 20T, 1 h ten Brink, G.-J.; Vis, J.-M.; Arends, I.W.C.E.;
%%
c1 I'hCIIO ,hC13 , SnC13 DCM, r t , 4 h
Hi>terocycle.s, 2000, 53, 1691.
Li, J.;
C ) - ( p - N = + N G
(CH2112
I
011
DMAP, DMAP-IICI, CHCI,
34% cis (8% truns)
Ph
(cHu
77% (+ 13% diolide) Keck. G.E.; Sanchez, C.; Wager, C.A. TclruherIron kjtt., 2000, 41, 8673.
c,eSH
338
Compendium of Organic Synthetic Methods, Vol 11
Section 123
PhI, cat CuBr ,toluene
\ /
=flux, 1-4h
Palorno.;Oiarhide, M.; Lbpez, R.;G6mez-Bengoa, E. Tetruhedron LEtt., 2000, 41, 1283. P~IB(OH)Z,1.5 CU(OAC)~* P S DMF, 3 eq Py , MS 4,4 reflux ,3 h Herradura, P.S.; Pendola, K.A.; Guv~.R.K. Org. Lett., 2000, 2, 2019.
0
2
N
0
0
M q S 0 4 , NaOH , 8 h PEG-400, heat
H
:
O
-
B uBr , CsOH ,I B A I
ph
Ph
SH
88%
N
O
O
M
-0Bu
Ph
MS 4 A . DMF ,23"C, 10 h
Dueno, E.E.; Chu, F.; Kim, S.-I.;
h
95%
Cao. Y,-0.; Pei, B.-G. Synth. Cornniun., 2000, 30, 1759. -011
z
P
92%
K.W, Tetruhedrnn Lett., 1999, 40, 1843.
PI,-
OH
P M 3 , ADDP , h - H
* Ph-s-I-ll 79%
ADDP = l , l ' ( a z o d i c ~ l ~ o n y l ) d ~ i ~ r i d i ~ i e Falck. J.R.; Lai, 1.-Y.; Cho, S.-D.; Yu, J. TetrulicJdronLett., 1999, 40, 2903.
X
, LiCD,MeN02
Montmorilloni telH20 l.t.2d Chlbl.;Hiram, T.; Kitano, Y.; Tnda, M. Chent. Contrnun., 1999, 691.
>99%
i-PrOH , zeolite-KMnO, Ph
*
OH
DCE, rt , 3 0 inin
Ph
oi-fi
9wo Gadhwal, S.; Boruah, A.; Prajapati, D.; Sandhu. J.S. Synth. Co/nmun., 1999, 29, 1921. PhSII
1 . Et,NIICl, MLCN , It, 15 min
2. EtI , overnight I'eroci, M.; Inesi, A.;
*
Ph-SEt
Sywth. Contnrun., 1999, 29, 261 1 .
93%
e
3 4
Section 124
339
Ethers from Aldehydes
,e- , A L ~ I I
97%
/
3M LiClO4, M e N q
OMe
bPh
OMe G i h a . K.; Fukuda, M.; Kim, S.; Kitano, Y.; Tada, M. J. Org. Chem., 1999, 64, 7654.
c ~ I ~ e , ; ~ ~ & p h
70%
Me0 Valenti. P.; Belluti, P.; Rampa, A.; Bisi, A. Synth. Cornriiun., 1999, 29, 3895.
P
h
o
\ /
O
BnBr , Cs2CO3 , DMF* P
H
h
e
\
O
B
23T,1h Synrh. Corririiun., 1999, 29, 4423.
Parrilsh, J.P.; Sudaresan, B.;
n 92%
1 . Mg , I2 , 1EflUx
* P hCH20CII2P h 80% 2. Tf*O,5"C Nishiyama, T.; Kalneyama, H.; Maekawa, H.; Watanuki, K. Cun. J. Chem., 1999, 77, 258. PhCIIzOH
SECTION 124:
ETHERS, EPOXIDES AND THIOETHERS FROM ALDEHYDES
Me1".C)-
P hCI 1 0
Me
, B n Br
, NaO I-I
t-BuOII , € 1 2 0 , 2 d
Zanardi, J.; Leriverend, C.; Aulwrt, D.; Julienne, K.;
J. Org. Cheni., 2001, 66, 5620.
PhSeSiMe, , PhH
*
4
&
h".
Ph
PhCH20SiMq 78 % Bu,SnI-I , cat AIBN XOC , 1 X h Kajiinoto, €1.; Kotani, K.; b c l a. N, Org. Lift.,2001, 3, 3087.
P hCI-IO
.. . . . m;
/
92%
Section 124
Compendium of Organic Synthetic Methods, Vol 11
340
M e 0 6)=Nz
PhCfIO
, 1% Rhz(OAc)4
DCM
*
Pha \
Dovle. M.P,; Hu, W.; Tinunons, D.J. Org. Lett., 2001, 3, 933.
Phff I 0
ph %,/
s,,,
66%
Ph
54% ( 9 4 5 &cmr:cis) 5%eeSS
W 0 3 ,r t , CHzClz Saito. T,; Akihu, D.; Sukairi, M.; Kanazawa, S. Tetruliedron Lett.* 2001, 42, 57.
MeCHO 0.1 M , hv, PhII * : H
+Ho>%
%%
19)
(8 1 eck. A.G.; Bondock, S. J. Am. Clic~m.Soc., 2001, 123, 6191. QSiEt3 -Rh catalyst, NSiEt, * o \ , \ , , , \ \ c o z M e C02Me
+
QSiEt,
O
P
0
2
toluene, 50°C
+
1) 2)
81% 81%
3. aq I I c l Teng, X.; Wada, T.; Okamuto, S.; Sato. F, Tetruliedron Lett., 2001, 42, 5501.
74%
RhCI(PPh& (3 Rh€I(PPh3)4 (1 Emiahata-Smith, D.; McKillop, A,; Mills, C.; Motherwell, W.B.; Synlctt, 2001, 1302.
+
M
e
Section 124
Ethers from Aldehydes
PhSH ,p-TS0I-I P 0. Y,;
I
0
Mihara, M.; Kawai, 1-1. Synlett, 2001, 1317.
341
q
54%
SPh
In(OTf)3, DCM ,0°C
h ( O T f ) ,, DCM Ptl-
95% (6.535 truns:cis)
CHO
40°C Ph b h . T.-P.; IIu, Q.Y.; Tan, K.-T.; Cheng, H.-S. Org. k i t . , 2001, 3, 2GG9.
Ph
/tPh
OsO, , K3Fe(CN), , K2C03 polymer-bound DIIQD-PHAL
Ph
t-BuOII, I120 , 0°C , 1X h
01r
92% (99% ee) Federov, A.Yu.; Cairara, F.; Finet. J.-P. T m a l i d m n Lett., 2001, 42, 5875.
72% Concellon, J.M.; Cuervo, 11.; Fein&ndez-Fano,R. Z'ctruhcciron , 2001, 57, 8983. PhCHO
PhCH=N-NTs- Na',
1% Rh2(0Ac\c4
20% tetrahydmthiophene , MLCN 20% BnNEt3CI,4O"C , 3 h
.r
A
ph
"I..,
Ph
95% (>98:2trunsxir) Almso, E.; I-Iyund, G.; Lydon, K.M.; Palmer, M.J.; Porceiloni, M.; StudIey, J.R. Angew. C h m . Int. Ed., 2001, 40, 1430.
;.K.V-
342
Section 125
Compendium of Organic Synthetic Methods, Vol 11
Me . I
92%
OMe
YrldrlY.; . , Reddy, B.V.S.; Kao, T.P. Tetruhedrnn L.ett., 2000, 41, 7943. PhCI-10 ,TIIF, r t , 3 d
m S i M e ,
i-Pr,
0.2
i-Pr
( Jy-pr N-PYIIIN: \,\ti'\
Wang, Z.; Kisanga, P.; w
PhCI10
e
*Amp 74%
a;x
. .I.G. J. Org. Clicm., 1999,64,6459.
Me$i-SnBu3
(8:l)
/
Ph
InCI, ,DCM Viswanathan, G.S.; Yang, J.; ]Li. C.-J. Org. L.ett., 1999, 1, 993.
(Jy --chr
4 q B n B r , O C , MeCN 2.8 eq NaOH , 2 1 h
l'm#l,
'"'F
PI1
ph
78% (92%ee)
Ph
Synlett, Z999, 1388.
IIayakawa, R.;
,,d"
P hCI 1 0
S
, 2 eq BnBr , 2 eq KOII MeCN-II20, rt , 1 d
-
Ph\,,\\\*'\ 92% (88% deB4% ee)
Julienne, K.;
SECTION 125:
1.
; Henryon, V.
J. CIWX SOC.,Perkin Truns. 1, 1999,731.
ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
Section 127
Ethers from Arnines
SECTION 126:
)(
Me
N,C021-Bu
343
ETHERS, EPOXIDES AND THIOETHERS FROM AMIDES
PhCHO , hv ,M C N
I
*
5h
Bn
RMe
Ph
N(Bn)COg-Bu
70% (2971 cis:truns)
Bach. T.; Schriider, J. Synthesis, 2001, 1117.
5) 58% conversion
(95
I\dam.;Stegmann, V.R. Synthasis, 2001, 1203.
PhCfIO
)==(
OlBDMS SePh
hv , MeCN
*YPh
OTBDMS SePh
81% ( 6 2 3 8 truns:cis) 80% conversion
Al.e.;Tachibana, K.; Fuji~noto,K.; Nojima, M. Synthesis, 2001, 1243. SECTION 127:
ETHERS, EPOXIDES AND THIOETHERS FROM AMINES
M5CI ICI-12C€120N0 MeZS2, MeCN
-
NO2 Allnire, F.S.; b y g a . J.W. Synth. Corrzrrrun., 2001, 3 1 , 1x57.
6 SMe
NO2
57%
344
Coiiipendiuin of Organic Synthetic Methods, Vol 1I
rBuOK ,b-BuOIf
Section 128
Ot -Bu
*
82%
IEflux
; Rajaiah, G.; Chandraiah, L.; Swamy, D.N. Synlert, 2001, 1779.
SECTION 128:
ETHERS, EPOXIDES AND THIOETHERS FROM ESTERS 1% [RuCIZ(CO)~],, EtI , 16 h 5% Et,NII, toluene, 100°C
OSiEt, 57%
Et,SiH * dOMe Terruheclrnri Lett., 2001, 42, 2149.
dOMe Igarashi, M.; Mizuno, R.;
-
OMe TiCh , TMSOTf, E1,SiI-I
ph? Yato, M.;
. 0
PhO -Me 0 DCM ; Ishida, A. Tetmhedron, 2001, 57, 5353. 1. i-BuZNII 2. PhSeH, Bh-OEt,
81%
SePh
91% (85:15 trunscb)
3. H Z 0
Schmitt, A.; Reissie. H.-ULSyrithc,sis, 2001, 867.
OCOzMe I
1. PhOH, THF Nd4MDS
PPh
1) 96% 1. Ph3SnII, PhZSA2, rt 0.5 BEt, , 1 h
2. N B N , 110°C MeO Ph D.0,; Song, S.H. Synlcrr, 2000, 811.
*
cat Cp*RuCl(cod) ,McCN BUSH,rt , 1 h
M e 0-Ph
94%
//\/SBu moCoZMe *
Kondo, T.; Moiisaki, Y.; Uenoyama, s.-y.; wada, K.; msudo. T,-~. J . Ani. C h n i . Snc., . l Y Y Y , 121, 8657.
97%
Section 129
Ethers from Ethers
Ph
345
2.2 ~q P h j S d I , rt BEt3 ,toluene 30 inin
97%
@?h
ee. DJ.; Leach, J.D.; Setiadji, S. TerruAerlron, I Y Y Y , 55, 2847.
SECTION 129:
ETHERS, EPOXIDES AND THIOETHERS FROM ETHERS, EPOXIDES AND THIOETHERS
A0
c IOII21
MqSiCl, hexane, 2 h sec-BuLilchiral diiunine -90"~- - 5 0 " ~
t
c 10%
/&jiMq 1
73%
Ifodeson. D . K ; Norsikian, S.L.M. Org. Lett., 2001, 3, 461.
CO,CMeCy, 1% CuOTf , EtOAc , rt 1.1%J S, S-his-fell-ocene heterocycles Lo, M.M.-C.; Fu. G . C , Tetrulic~clron, 2001, 57, 2621.
ph
Ph2CH-OMe
C J I P H , Fe(C104)7
7496484: 16 cis:truns)
*
Ph2CHOC3H7
97%
reflux, 150 inin
Salehi.;Irandoost, M.; Seddighi, B.; Behhohani, F.K.; Tahmasebi, D.P. Synth. Coniriiun., 2000, 30, 1743.
PhS
w
I-(CI12)s I , NaNI12-DME
0°C , 2 h
-
75%
Choppin, S . ; Gros, P.; Fort. Y. Syntlz. Conirnun., 2000, 30, 795. I'
1. 1.5 ec1 BuLi, 'I1IF ,-78"C 2 . 3 eq L i c l ,-78°C ..-, 0°C
5 Ph
Komine, N.; Tomooka. K.:
Hetemcyrles, 20011, 52, 1071.
63% (86:14 truns:cis) S.574 ee 1 for hob
346
Section 129
Compendium of Organic Synthetic Methods, Vol 11
m S i M e 3
,-5o*c
SnQ. CI-IzClz
OBn
79% (1:l &:trans)
a; Kimura, Y.; Yokie, I. Tetruhedron Lett., 1999, 40, 5877. M
e
\ 0/
\e /
M%CCH,I, TIIF,2 eq EtMgBr rt , 5 h * M
0 MgBr
Inoue, A.; Shinokubo, H.;
SiMq
w
76%
Synlett, 1999, 1582. TMSN3, PhH
o
os
Mn den-iinrnol~ilizd inesoporous meterial Kantarn.;Choudary, B.M.; Barathi, B. Syntlz. Conimun., 1999, 29, 1121. 0 . 2 Sn(PPh3)(ClO4)z ,MeCN* (NHz)2CkS,reflux , 4 5 min
93%
; Mirkhani, V. Synth. Conimun., 1999, 29,
EFIo
2.5
Ph\/\/
S d 2 , THF-HMPA
*
2.5 eq TES-CI
IIonda.;Ishikawa, F. Syntlt.
Ahe.;Koshiha, N.; P
h
q
oor. N... T;-.
o
.
2079.
Contntun., 1999, 29, 3323.
Yamasaki, A,;
OSiEt,
ph\/\/
97%
eterocycles, IYYY, 5Z, 2301.
NHJCN , P4VP-Ce(OTf)4
*
P h q s MtCN ,i t , 15 inin Shekuiriz, M. Syntlt. Cornmim., 1999, 29, 3313.
90%
Section 130
Ethers from Halides
341
REVIEWS: "The Brook Reanangement In Tandem Bond Fonnation Strategies," Moser. W.H. Tetruhedron, 2001, 57, 2065.
SECTION 130:
B
e
C
Parrish, C.A.;
ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATES NaOt-Bu ,cat Pd(OAch, 100°C toluene , phosphine ligand
l
B
\u /
92%
J. Org. Client., 2001, 66, 2498.
'
O Or-Bu
BuOI-l, 2%Pd(OAc), 2.S% phosphine ligand toluene, 2.5 eq Cs2C03 Torraca, K.E.; Huang, X.; Punish, C.A.; Bchwald. J. Am. Chem. SOC., 2001, 12.3, 10770.
a
NMP ,70"C, 6 h 88%
NO2
Gujadhur, R.;
oc"'
Synth. Comnzim., 2001, 31, 2865.
- &Q
1. i-PrMgBr, T I I F , -10°C
2. PhCIIO ,-10°C
reflux
/
Ph
82%
Delacroix, T.; BCrillon, I-.; Cahiez. G.; Enochel. P. J. Org. Clietn., 2000, 65, 8108.
C S 2 , NaBH,, TIIF Wan, Y.; Kurchan, A.N.; Barnhurst, L A . ;
Org. Lett., 2000, 2, 1133.
Section 132
Coinpendiurn of Organic Synthetic Methods, Vol 11
348
PhSeSnBu:, , toluene, 80°C 5% Pd(Ph3), * Tokunaga, K.; Sonod a. N. Org. LEtt., 1999, 1, 1725. Related Methods: Section 123 (Ethers fmm Alcohols).
SECTION 131:
ETHERS, EPOXIDES AND THIOETHERS FROM HYDRIDES NO ADDITIONAL EXAMPLES
SECTION 132:
ETHERS, EPOXIDES AND THIOETHERS FROM KETONES
Kang, T.; Scheffer. J.R. Org. Lett., 2001, 3, 3361.
d
PI
Ph Ma, Y.;
PI1
85%
Ph
Sin12, S i n , it , 2 0 inin
Ph
Ph
s; Chen, .I. Synthesis, 2001, 1004. C&I ITOH, Pd/C , Hz s t E m 105°C
Chent. Lett., 2000, 926.
Fujii, Y.; Furugaki, H.; Yano, S.;
[t-BuSiMezCFBrzA3uLi]
*
Ph
THF
97%
r-BuMe,Si
. . -M.;IIata, T.; Hiyama, T. Heterocycles, 2000, 52, 707.
94%
Section 1.74
Ethers from Akenes
CHCI, , NaOII , TEBA
349
+I:
Ph Ph
z
Ph&Ph b s t e li. '; Romaliski, 1.; Swiatek, A,;
80%
H d v . Chirn. Actu, IY99, 82, 946.
Related Methods: Section 124 (Epoxides from Aldehydes).
SECTION 133:
ETHERS, EPOXIDES AND THIOETHERS FROM NITRILES NO ADDITIONAL EXAMPLES
SECTION 134:
ETHERS, EPOXIDES AND THIOETHERS FROM ALKENES ASYMhlETRIC COMPOUNDS 2
O X O W, 4 eq NaZC03
chir al a inm)nium s3 It -alcohol MLCN/I1,O
64% (30%ee)
; Rassins, G.A.; Bairos, D.; Ardakani, A,; Buckley, B.; Bethell, D.; Smith, T.A.D.; Slawin, A.M.%. .I. Or.CIWIK,2001, 66, 6926.
A
4 '
[ R ~ ' ~ ( D ~ - € t i r * ) C,lPhH, ,] rt
* 75% (70% ee) Sol-Gel-silica , 2 d I'h Zhang, R.; Yu, W.-Y.; Wong, K.-y.; Che. C.-mJ. 01-8.Chwz., 200Z, 66, 8145. Ph
w
Ph
Cr salen catalyst , PhIO Ph3P0
A0
Ph
,\\"
,,+"
4S% (92% ee)
Daly, A.M.; Renehan, M.F.; Gilheanv. D .G, Org. Lett., 2001, 3 , 663.
--/
Ph7
Cr-salen coinnlex 0°C MeCN, Ph;P=O
''I,,,
72% ee '4,
O'Mahony, C.P.; McGanigle, E.M.; Renehan, M F . ; Ryan, K.M.; Keirigan, N.J.; Bousquet, C.; y. D.Cr, or& k t t . , 2001, 3, 343s.
350
Compendium of Organic Synthetic Methods, Vol 11
Section 134
0.1 r-BuCHgIIO , 3 h , it
0.1 bis-amidopyrrolkline
/
Ph
MtCN ,NaHC03 , H 2 0
Ph 93% (65%ee) 80% conversion Org. k t t . , 2001, 3 , 2587.
n; Ho, L.-M.; Zheng, Y.-S.; Ho, C.-Y.;
Lh * L 5% (R) Ln catalyst TBHP - d ~ i ~ ~ e
Ph
99% (96% ee)
, , , , #$
MS 4 A , TIIF, 25 nun
Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shihasaki. J. Am. Cheni. Soc., 2001, 123, 2725.
Ph
Ph
M,
-a
1.20% La-S-BINOL-O=AIPh3complex 2.4 eq TBHP , toluene, T H F
dN kN4
Ph
2.MeOH
MS4.4,lt
& =
Q
O Me
Ph
86% (91% ee)
Nemoto, T.; Ohshima, T.; Shihasaki, M. J. Ant Cheni. Soc., 2001, 123, 9474.
A
Ph
Mn salen catalyst , NaOCl CH,CI, , Na,IIPO, (pH 11.3) 4-phenyl pyiidine N-oxide
/99% after 21 h) Syrilett, 2001, 1305.
van Vliet, M.C.A.; Arends, I.W.C.E.;
PhSH ,PhH , 80°C, 1 d
A
Ph
-
+
Ph
SPh
Ph-sph
2% 97% + inontinoiilbnite K10 80% 6% Kanagasahapathy, S.; Sudalai, A.; Benicewicz, B.C. Tetrulierlron Lett., 2001, 42, 3791.
W s s e l . h;A n d w e , M.K.M. Tctruhedron Lett., 2001, 42, 2293.
Ph
knherlyst A-26(011-) , H202 dioxane , rt , 65 h
0
*
ph%rph
96% 0 Lakoura-i. M.M.: Movassaph. B.; Bahrami, K. Syntlz. Corirniun., 2001, 31, 1237.
S'
N II N
CD3CN, 25°C. 15 h
+
bS 45%
& a n . W.; Bargon, R.M. Eiir. J. Org. Chmi., 2001, 1959.
+w
aniphiphilic sugars, H20, , M o + ~ OH
ori
2"C, I d
Denis, C.; Misbahi, K.; Kerhl, A.; Fel-rikres, v.; Chenz. Cnrrmrtn., 20U1, 2460.
75% * ?
Section 134
357
Ethers from Alkencs
Fbse)2
cat F3C
Bu
cat NaOAc, 60% 1 1 2 0 2 , 1 h CIi3CH,OI1,2OoC ten Brink, G . 4 . ;Fernandes, B.C.M.; van Vliet, M.C.A.; Arends, I.W.C.E.; J. Chein. Sor., Perkin Truns. I, 2001, 224.
Bu"v
74%
Bu\ TiC$-NMe,, DCM -78°C
w
t-Bu
(90 SjGholm, IIeilunerling, hl.; Pradeille, N.;Somfni. P. J. Chcni. Soc., Perkin Ti-trris. 1, 2001, 891.
x.;
a
10)
quant
e:% I
80%
Pitts, M.K.; IIarrison, J.R.; Moody. C.J. J . Cherit. Soc., Perkin Truns. I , 2001, 955. 0.2.5 S x , cat Mo(O)(S,CNEt,),
acetone. 5 6 T , 15 h
Sinha, J.; Layek, S . ; Mandal, G.C.;
*
+.
+ 20% cyclooctene C h i . Conintun., 2001, 1916.
10 atin N 2 0 , PhCl , 140°C 5 % Ru-porphyrin c o m p k x
63%
Yamada, T.; Mashirnoto, K.; Kitaichi, Y.; Suzuki, K.; keno, T. Claem. Zxrt., 2001, 268.
358
Coinpendiuin of Organic Synthetic Methods, Vol 11
Section 134
CHCl, ,FeS04, Si02 ,31"C
Ghorbani, M. Mona?. Chcm., 2001, 132, 989.
;-
Legms, J.; Crousse. B,;Bourdon, J.; Bonnet-Delpon, D.; B6gu6, .I.-P. Tetruheilrnn Lett.. 200Z, 42, 4463.
.I
S8% (+ 45% acebphenone)
Iwahama, T.; Sakaguchi, S.; Jshii. Y, Hctcrocycles, 2000, 52, 697. Oxone , MeCN-aq EDTA, rt P
h
m
p
h
b
polymer-hound ketone
Afi
=a Ph
Sonp.; Liin, J.S.;Kim, S.C.; Lee, K.-J.; Chi, D.Y. Chein. Commun., 2000, 2415.
nA
Ph
2a 1 Illcpha , CHzC12, -78°C 5% CU(M&N)~PF~ ,8 h
Ph
77%
Andrus.;Poehlein, B.W. Totruhtdrnn Lett., 2000, 41, 1013. H202
94%
, NLIIICO~ , DZO ,25"C 70% conversion (99%)
Yao, H.; &&~dson. .. .
m
Ph
ph
I>&
J. Ani. Chew. Soc., 2000, 122, 3220.
4 ~ X J PhCIIO , B&t,NCl, It
ALfi
1.1 q chloramine M , 1 d * Ph Yanp,; Zhang, C.; Wang, X.-C. J. AJH.Chein. Soc., 2000, 122, 4039.
63%
Section 134
359
Ethers froin Alkenes
BIIOCII~CHO,-78°C BF3*OEt2,DCM
oms 7x76 (>20: 1)
Ph Micalizio, G.C.; Koush. W.R. Org. Lztt., 2000, 2 , 461.
A
30% aq H202, LiOH-Ii20, It ph ether, polymer-hound quaternary Ph iunmonilun salts ,20 h Anand, R.V.; Sinch. V.K. Synlett, 2000, 807. 1 % MeReO,, ~ 2.5
Bu*Bu
TFA
-
d ph
p
9
8
*
2.5 eq Na percarbonate, 6 h 12% pyr u o k J . Org. Chcni., 2000, 65, 4210.
w
c5111 1
O2 , tetrdin , PhEt , PhCN 60°C. 2 h
85%
*
10%~ N-hydroxyphthalimnide
0.1% C o ( 0 A c ) ~, 5% Mo(C0)6
Iwahama, T.; Hntta, G.; Sakaguchi, S.;
fi*
Ph
%
CdI1 I
79% (99:1 trunscic.) Chcni. Corrnnun., 2000, 163.
30% aq H 2 0 2 , acetone 0.1% Mn20(0Ac)2(TPTN) * FhhI'h Chcrii. Conniirm., 2000, 537.
Brinksma, .I.; IIage, R.; Kerschner, J.;
Owens, G.S.; Ahu-Oinar. M .M, Chenr. Conirnun., 2000, 1165. 0 1I
I
Me?C(CphTiCl, ,t-BuOOH ,28 h hexane ,6O"C
n
Ph'
OH I
X0% (44% erythro:rhreo) Sala, G.D.; Giortl:ino, L.; Lattnnzi, A,; Porto, A,; S c r e t u Tetrulterlrori, 2000, 56, 3567.
3 60
&f
Compendium of Organic Synthetic Methods, Vol 11
II 0
-
Section 134
Oxone, 0°C,30min acetone, NaIICO,
91% (2:3 a$)
Ferraz.,Muzzi, R.M.; de 0. Vicra, T.; Viertler, H. Tetruhchm LEtt., 2000, 41, 5021.
Ph
COzEt
1 0 . E :
, 10% Oxone
ph
KIISOs. NaIICOq, MeCN irq Na2EDTA ,-Z h ;Hayter, B,R.; Moss, W.O.; Reeves, J.R.; Wailer, J.S. Tetrahedron A . Y ~ I ~ I2000, I I I . , 11, 2M7.
8
60% 1 1 2 0 2 , c q c I r 2 o I I
quant
99%.
6 0 T , 20h Neimann, K.; Neumann, R. Org. Lett., 2000, 2, 2861. M%CIICH2CIIO1O2 DCM , Pd/Si02, r t , 6.5 h
98%
Gao, 11.; h c e l i c i . R ..I Syntli. . Cornnirin., 2000, 30, 1230. c o catidyst ,60°C
96%
M5CCI I( Me)CI I=C€12 Hunter, R.; Turner, P.;
e.
Syntli. Conzinun., 2000, 30, 4461
30%~ XIH202 ( 2 eq), 0.5% M c R Q
A
A0
* 97% 10% 3-fluoropyridine1 DCM Ph Molfsson. IL;Copbret, C.; Chiang, J.P.; Yudin, A.K. J. 01-8.Chern., 2000, 65, 8651.
Ph
w
Ph
Shu, L.;
11202 , CF,COMe, MeCN K2CO3
J. Org. Cliem., 2000, 65. XXO7.
93%
Section 134
Ethers froin Alkenes
36 1
modified S O , Sakamoto, T.; Pac. C. Tc.tru1iedronLett., 2000, 41, 10009.
2 eq Oxone ,pymlidine ,0.5 Py MLCN , 10 eq NaHC03 Adamo, M.F.A.; h a r w a l . V.K.; Sage, M.A. J. Am. Clieni. Sor., 2000, 122, 8317.
Ti(OCH2CI IzOh
H O-
hexane, 16 h
Massa, A.;
w
Ph
6%
-
OH 47%
Synlett, 2000, 1748.
0.1
BFi
-A
oo
Ph Oxone, 4 eq NaHCO, ,25”C * 81% aqMeCN, 16 h Minakata, S.; Takemiya, A.; Nakamura, K.; Ryu, I.; J(omatsu. M. Synlett, 2000, 1810.
Bu@, 60% H i 0 2 in CF3CII20II 2% I’~As(C:I-I~CI-I~C~H,,)~ ,reflux
-
95% van W e t , M.C.A.; Arends, I.W.C.E.; w o n .R.& Tetruhedron L z f t . , 1999, 40, 5239.
y. Ph
Oxone , aq MLCN Ph/Jh
Ph
30% Bn-N
)- N\ Bn
0
Carnell. A.J.; Johnstone, R.A.W.; Parsy, C.C.; Sanderson, W.R. Tetruhedron Ixtt., 1999, 40, 8029.
70%
-
362
Coinpendiurn of Organic Synthetic Methods, Vol 11
Section 134
MgioAh(OHhCO,, JXE
* C 5 30% aq H z q , i-PiCONH2 Na dedwyl sulfate ,70"C , 1 d Yamaguchi, K.; Ebitani, K.; Kaneda.K.. Org. Chern., 1999, 64, 2966. C5Hl1
H
l
l
w 0
80%
moist MMPP DCM,7h MMPP = inonopeiuxyphthalic acid Foti, C.J.; Fields, J.D.; &opp. P..I, Org. Lett., 1999, 1, 903.
w
Novozy1l1-435, HZO,
CSHI 1 ;-
0
.. .
=-
(MeO),C=O
C
5
H
I
67%
WarweI, S. Or#. Lett., 1999, I , 1025.
l 0
Do D
60% 11202, C ~ F I ~ B I . / P,70"C ~H Ct1Fi7
SeBu
L-
92%
5% C8F17
Betzemeier, B.; Lhermitte, F.; h o c h e l .
A
E Synlett, 1999, 489.
PhSII , II-Rho-zeolite , 5 h
Ph
*
hexane , 7 h Kurnar.; Pandey, R.K.; Iiegde, V.R. Synlett, 1999, I921 I-1202, DCM-EtOAc 5% perfluomheptadwan-9-one
van Vliet, M.C.A.; Arends, I.W.C.E.;
van Vliet, M.C.A.; k e n d s , I.W.C.E.;
~
Ph
SPh
0
Cherrt. Cnlnrnun., 1999, 263.
21 h
>Y9%
Chent. Conznzicn., 1999, 821.
69%
Section 135
Ethers from M i x .
I1
363
I12/C0 (400 psi) ,PhII [Rh(OAc)J,, 20 h 80%
OH Bergmann, D.J.; Campi, E.M.; u s o n . W.& ; Patti, A.F. Chem. Commun., lYY9, 1279.
&Ph
Ph ;-
Oxone, NaHCO, , H 2 0
*
MeClN , 10% chiral iminium salt
PhA
L
P
”
89% Ahned, G.; Garnett, I.; Goacoleu, K.; Wailes, J.S.Tetruherlron, 1999, 55, 2341.
amino acid-Schiff base Mn complex
\ - uB
0 2
,8O”C, 11.5 h
Wang, R.-M.; IIao, C . 4 . ; Wang, Y.-P. Syntli. Cornmun., 1999, 29, 1409.
SECTION 135:
65%
ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS
4’”’
1.5 “1 HGaCl, , BEt,
-&+Yo
THF ,0°C , 3-5 h
c,
c, 117 137 97% (84:16) Mikami, S.; Fujita, K.; Nakamura, T.; Yoiiiiiitsu, 11.; Shinokuho, H.; Matsuhara, S.; Qshima Org. Lrrtt., 2001, 3, 1853.
. ddv. . JS,; Subha Iteddy. B.V.; Srinivas, C.; Srihari, P. Syrtlett,
JhdsrLK; ,> de S 6, A.C.P.F.;Mcnczes, P.H.; Gonplves, S.M.C. Tetruhedi-on Lctt., 2001, 42, 4597.
20OZ, 854.
h P
364
Section 134
Coinpndium of Organic Synthetic Methods, Vol 11
A
Ph
PhCHO , Rhz(OAc), ,rt , 1 h CO2Me
* A ,l,llI\
Ph
hexatldCH2C12
76%
Davies. H .M.L.; De Meese, J. Tetruhedron Lett., 2001, 42, 6803.
1 . CpzTiH
TolSSTol
t
2. PhzI'X- ,TIIF-HMPA , 60°C Huane.;Wu, L.-L.; Xu, X.-11. Synrh. Carrzrtiun., 2001, 31, 1871.
0
HO II Ph VSVPh
OH
+
TolSPh
ph
02Me
78%
hP,Ph ,S, ,
MeCN , reflux, 4 h
98%
Miller, S.J.; Collier, T.R.; Wu. W. T e t r u l i ~ h mLett., ~ 2000, 41, 3781. 0
It PhNs\
2 eq TiC14, MeCN Ph
*
0°C. 15 inin
PhNs\
Ph
94%
. . Shlmlzu.; Shihuya, K.; Hayakawa, R. Synlett, 2000, 1437.
o(N:Et i
TMSXkPh , M a H
0
DCM
Abe.;Fujii, 11.; Yumasaki, A.; Kinome, Synrh. Coniniun., 2000, 30, 543.
76%
*
..
Y.; Takeuchi, Y.;
0 2
NaOH , TIIF, MLQII it,lh
'
-
Ph; Joo, Y.II.; Cho, 0
It
*
Ph) P h
+, ,#' '
86%
D.11.Syntk. Corrvriun., 2000, 30, 4489. WC16/Zn/THF, 10 inin
PhNs\ Ph J'irouzahadi. 1-1.; Karimi, B. S y n t h ~ s i s I, Y Y Y , 500.
t
PhSPh
96%
Section 135
365
Ethers froin M i x .
b Pb
P h 3 S n I I , AIBN , PhH 80°C
Crich. D.X.; IIuang, X.; JVewcomh. M. Or#. Lcjtt., I Y Y Y , I, 225.
95%
93% Genski,T.; Macdonald, (3.; Wei, X.; Lewis, N.; Tavlor. R.J.K. Synlett, ZYY9, 795. m S i M e 3
,BnOTMS
0.3 TMSOTf , MLCN, -20°C , 3 h
Suzuki, T.; Orivaiiia. T. Syntlz. Cornn,rm., Z999,29, 1263
L ,
Ph
57%
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 10
PREPARATION OF HALIDES AND SULFONATES
SECTION 136:
HALIDES AND SULFONATES FROM ALKYNES NO ADDITIONAL EXAMPLES
SECTION 137:
HALIDES AND SULFONATES FROM ACID DERIVATIVES 3 ecl Oxone, reflux, NaBr , 3 h
Ph-Co2H
iq MeCN , Na2C03 ,rt
-Br
t
88%
Ph
YOU,H.-W.; Lee, K.-J. Synlerf, 2001, 105.
NBS , MeCN , LiOAc
Br 42%
Jung, I.-H.; Lee, H. Tetruhedron Lett., 2001, 42, 1065.
p b m C 0 2 H
R a t ; Guin, C.: Maiti,
LiBr , aq MeCN , CAN ,it G. Tetruhedron k i t . , 2001, 42, 9253. NazMoO,, KBr , HzOz
Ph*m2rr Sinha, J.; Layek, S.; Mandal, G.C.;
t
1r20
* Ph*Br
mBr
Ph
Cheni. Coinniiin., 2001, 1916.
65%
Section 138
m
Ph
367
Halides froin Alcohols
C
0
2
1
NBS , LiOAc , M&N,
1
I-120
micmwaves , 1 min
&Br
-
Ph
84% ( 9 5 5 E:Z) Kuang, C.; Senboku, 11.; Tokuda. M, Synlett, 2000, 1439.
=
Ph
N-iodosuccinimide 10% B u ~ W - O ~ C C F ~
*
COZH
P
h
CH2C12, 15 min
-011
bmiC1= ionic liquid
It,
*
Id
a-
Ren.;Wu, J.X. Or$. Lett., 20U1,3, 3727.
r
+ succinimide
HALIDES AND SULFONATES FROM ALCOHOLS AND THIOIS hiniCl , MeS03H
PhcH,or
1
99%
Naskar, D.; Buy. S.I. Orx. Chern., 1999, 64, GX96.
SECTION 138:
=
BF,-OEt,, KI ,dioxllne /
98%
-
PhCI 121
it , 5 inin RU&l,.LBJLB.P.;Sadavarte, V.S.;LJppalla, L.S. Zetrdzedron L a , 2001, 42, 951.
.
NBS , PPh, ,CII,CI,
Ph 1t,5h Iranpoor. N.; Firouzilbadi. 11.; Aghapour, G. Synlett, 2001, 1176. Ph-s11
Br
95%
78%
ChCCCI3, diphos , rt
TIIF,3 h Pollastri. M.P.; Sagal, .IF.; Chang, G. Tetruhedrnn Lett., 2001, 42, 2459. P 2 0 5 , Bu,h%r,
toluene
100"C, 1 h Kato. Y.; Okada, S.; Tomimoto, K.; Mase, T. T'etruhedron Zxtt., 2001, 42, 4840
MeSO,II, N d , DCM
* PhCltI reflux, 15 min Kam.; Kamesh, G.; Laxinan, N. Synth. Corntnun., 2001, 31, 827. PhCI 1 2 0 € I
92%
Coinpendiuin of Organic Synthetic Methods, Vol 11
368
IF5 , Et,N-3 KF ,heptane
CIOHZ1 -OH
Section 139
C~oHz~-F
32%
80T,2 d Yoneda.: Fukuhara T. Clienz. Lett., 2001, 222. CeC13-7 H@ , NaI
T O I 1 MeCN , reflux Di Deo, M.; : Tonegiani, E.: . J. Orb. Cherii., 2000, 65, 2830.
I
-
48%~€IBr
HO( CHZ)xOI1
89%
; Bellucci, M.C.; Bosco, M.: Sambri, L.
85%
IIO(C€12)aBr cyc lohexane J.M.; IIeuft, M.A.: Rahhat, P. J. Org. Chenz., 2000, 65,5837.
w.
MqN=C(CI)SPh C I , DCM C,Hy-OH LC*IIy-C1 97% Gomez, L.: Gellibert, F.; Wacner. A.: Mioskowski. C. Tetruherlron Lxrt., 2000, 41,6049. TSCl, MqN(CIIz),NM%
C~II~~CII~~TS 94% MeCN , 10°C Yoshida, Y.; Shimonishi, K.; Sakakura, Y.; Koada, S.: Aso, N.: Synthesis, 1999, 1633. C7H pjCH20II
Me-N 5J
0 1 4
CJ
l a -
N Me t
NEt, , CHzCl2, It, 12 h Isohe, T.; Jshikawa. T. J. 01-8.Cliciii., I Y Y Y , 64,5832.
P hCH2OH Chaudhari, S.S.;
SECTION 139:
SOC12 , benzotriazole , rt
2'
93%
t
PhCHzCl
diy D C M , 10 inin Synlett, I Y Y Y , 1763.
95%
HALIDES AND SULFONATES FROM ALDEHYDES
BC13, hexane, reflux PhCIIO G.W,; Wu, Z. Tctrulicdron LL'tt., 2000, 41,579.
t
Ph-CHClz
90%
Section 143
369
Halides from Esters
cyclohex yl-BBr , hexa ne
P hCI-IO
PhCIIzBr
e
85%
1t,3h Kdbdlka.; . . Wu, Z.; Ju, Y. Tetruhedron Lett., 2000, 41, 5161.
P hCHO
BuBC12,Oz , hexme
* B u' 2h,rt Ph Kabalka. G.W; Wu, Z.; Ju, Y. Tetrahedron Lett., 2001, 42, 6239.
SECTION 140:
52%
HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLS
For the conversion R-I-I + R-Halogen, see Section 146 (IIalides from Hydrides). NO ADDITIONAL, EXAMPLES
SECTION 141: HALIDES AND SULFONATES FROM AhlIDES NO ADDITIONAL EXAMPLES
SECTION 142: HALIDES AND SULFONATES FROM AMINES NO ADDITIONAL EXAMPLES
SECTION 143: HALIDES AND SULFONATES FROM ESTERS (3
0.01% hexaliutylguanidinum chloride
115°C-
93%
12OoC,4h
Violleau, F.; Thi6haud. S.; Borredon, E.; I,e Gars, 1'. Synrh. Cornmun., 200Z, 31, 367. 70% IIFPy, NIS , DCM
-OMe
\ /
KI3r ,30%1rzoz, It
Narender, N.; Srinivasu, P.;
M
98%
I ; Raghavan, K.V. Syntlz. Comniun., 2000, 30, 3669.
, NdO, , HZSO,
t
AcOH , A q O Bicll. Clwni. Snc. Jpn., 2000, 73, 951.
Ph-r
65%
NC
Zdnkd.; , . Kuhota,
98%
A. Synlett, ZYYY, 1984.
96%
374
Compendium of Organic Synthetic Methods, Vol 11
.o
NaOH,CHI3,1d , r t
Schremer. P .&, Lauenstein, 0.;Butova, E.D.; Angew. Chcni. Int. Ed., Z999, 38, 2786.
t
. .
(PhM%Si),Cu(CN)Liz
TIJF, -78°C
4
rt
Section 148
v'
*
92%
SiMezPh
*
75%
ns, M.; u d f o r d . G .; Skinner, C.J.; Atherton, M.J.; Moilliet, J.S. J. Chern. SOC.,Perkin Trans. 1, 1999, 803.
t-BuOOI-I, HBr , HzOz
Barhate, N.B.; Gnjare, A S ..; -
A.V, Tetruherlon, 1999, 55, 11 127.
QBr
NBS , AcOH, 8 min
91%
Bu Hoffinann, K.J.; PhII Luliliski, P.;
I Synth. Connnim, Z999, 29, 1607.
HzSOj, MnOz, Iz
+
AcO1-l , AQO , 10°C BuII. C h m . SOC. Jpn., Z999, 72, 115.
PhI
Bu
63%
Toea.; Abe, S.; Nognmi, G.; Yokoyama, M. Bull. Chent. SOC. Jpn., Z999, 72, 2351.
SECTION 147:
HALIDES AND SULFONATES FROM KETONES NO ADDITIONAL EXAMPLES
SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLES
Section 149
375
Halides from Alkenes
SECTION 149:
HALIDES AND SULFONATES FROM ALKENES
For halocyclopropanutions, see Section 74E (Alkyls from Alkenes). 0
Mg(ClOdh, BEt3/0, chiral his-oxazoline catalyst
%,,,
t
CO,Et
toluene, -78C, 5 h
A
%67%
(94% ee)
Yane.;Gu, S.; Yan, Y.-L.; Zhu, N.-Y.; Cheung, K.-K. J. Am. Clzenz. Snc., 2001, 123, 8612.
-
chiral R u catalyst, CCl, \P +h
Slmdl.;Wlodarczak, L.;
i Bu
rt, I d
Ph
90%
; Noels, A.F. Eur. J. Org. Chemi.t 2001, 2689.
Me ,N C
d I 4- C1
C1
Ar
*
h v , MeCN Ar = 4-dimethyl~inopheiiyl
131.1 35%
18%
Mella, M.; Coppo, P.; Guizzardo, B.; Fagnoni, M.; Freccem, M.; Alhini. A. J. Org'. Cficvii., 2001, 66, 6344.
4
1. S% Cp2ZrClz , ~ I I 1 7 0 T s 'IIIF, 55°C
@M@r
*
2. NBS , 0°C
de Annas, 1.;Hoveyda. A.H. 01.8. In.tt., 2001, 3, 2007.
/--/
Phc 73%
Ph
c5r11 1
Bu
zirconium dihydrate magent t
TIIF, r t , 4 h
Wipf. P.; Wang, X. Tetrahedron fxtt.,21100, 41, 8237.
x:I Br
C511,1
CS%I
82%
Section 150
Compeiidium of Organic Synthetic Methods, Vol 11
376
NaN3, NaI ,CAN, Me011 0°C , 3 0 inh
70%
Nair. V,;George, T.G.; Slieeha, V.; Augustine, A,; Balagopal, I..; Nair, L.G. Syrilett, 2000, 1597.
quant
Tallnrico, J.A.; Maltlick, L.M.; Snanner. M.1,. .I. C?rg. Client., 199Y, 64,344.
-
Mg 30% silica-supported Cu catalyst DCE, reflux, 18 h 0
0
I
I
Ts
TS
94%
Clark.,Filik, R.Y.; IIadclletoon, D.M.; Radiguc, A.; Sanders, C.J.; Thomas, G.U.; Smith, M.E. J. Org. Climi., 1999,64,8954.
SECTION 150:
3 +
HALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS
N, BF,
Br
N%PdCI,, 75% MeOlI, 40°C
B -*,:p,
0
Willis, D.M.; ,Ctronrin. R.M. Tctmhedr-nn Lett., 2000, 41, 6271.
Br
56%
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 11 PREPARATION OF HYDRIDES This chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen: e.g. RCIi2X -+ RCII2-I1 or R-H.
SECTION 151: HYDRIDES FROM ALKYNES NO ADDI'IlONAI, EXAMPLES
-
SECTION 152: HYDRIDES FROM ACID DERIVATIVES This section lists examples of decarhoxylations (RCO2II
m i a ~ ~ w a v e15 s , min
*
-
R-H) and related reactions.
CO,H 98%
Ph
COZH 190°C Zara, C.L.; Jin, T.; Giguere. R.J. Synth. Coriiririrn., 2000, 30, 2099.
-
SECTION 153: HYDRIDES FROM ALCOHOLS AND THIOLS This section lists examples of the hydrogenolysis of alcohols and phenols (ROH
InC:I, , 2 a 1 Ph,SiIICl, DCM rt,2h Ph Yasuda, M.; Onishi, Y.; IJeba, M.; Miyai, T.; Baha.
pll
Ph
I>h
* Ph
Ph
-
87%
4.J. Org. Cherii., 2001, 66,7741.
H3PO2, cat 1 2 , AcOII 60°C
Gordon, P.E.; Fiv. A.J. Tetruhadrori L.elt., 20111, 4 2 , 83 I .
-
Ph-Ph
'Iuant
R-11).
378
Compendium of Organic Synthetic Methods, Vol 11
Section 157
cat Co(0Ach
85%
C r u d u C.M.; Allen, D.; Mikeluk, M.D.; Sun, J. Chenr. Cornniun., 200Z, 1154. Also via: Section 160 (Halides and Sulfonates).
-
SECTION 154: HYDRIDES FROM ALDEHYDES For the conversion KCI-10
R-Me, etc., see Section 64 (Alkyls from Aldehydes).
NO ADDITIONAL EXAMPLES
SECTION 155:
HYDRIDES FROM ALKYLS, METHYLENES AND ARYLS
H~(OAC)~,TBM ~
.to+
1:l THFMeOH Poliskie, G.M.;
SiM%Ph 48% M.M .; van Well, R. Tetrahedron Lett., 1999, 40, 589.
SECTION 156: HYDRIDES FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 157: HYDRIDES FROM AMINES
a
This .section lists exuiiples of the conversion RNH2 (or R2NH) + R-H. 1. MeSO2C1, Py 2. NaH ,NH2Cl
Wang, Y.; Guziec Jr.. F.S. J. Org. Chciii., 2001, 66, 8293.
96~87%
Section 158
Ilydrides froin Esters
379
NI-I NaNO2, AcOH ,EtOH
6
80%
i q Na hisulfite ,It, 20 h
1
Geoffroy, O.J.; Morinelli, T.A.; Meier. G.B. Tetrulzedron Lett., 200Z, 42, 5367. 2 q L i , ’ P I F , l d,rt P
h
\ O/
* P
e N Mez
h
O
a
\ / yuant
Azzena, U.; Dessanti, F.; M m i . G.; Pisano, L. Z’etruhedron
Zm.,1999, 40, 8291.
SECTION 158: HYDRIDES FROM ESTERS This section lists exainpIes of the reactions RC02R‘ -t R-H and RC02R’ + R’H.
-JOT HcO2N H2 at b 3 (CO) I2
N
Ph
dioxane , 160°C 20h
/
* P h
n 76%
Chatani, N.; Tatarnidani, EL; Ie, Y.; Kakiuchi, F.; J. Ant. Chpni. Soc., 2001, 123, 4849.
Ph2SiH2,(t-BuO),
*
68%
140”C, 20 h ; Kim. J.; Cho, D.H.; Chung, C.-M. Tetruhedron Z.m,
b
COZEt
Yu, Y.;ZhngJ.
1 . 10%CpzTiClz, TIIF i-PrMgBr ,rt , 4 h 2. 2N FIC1
Synrh. Coiirrrirm., 1999,29, 243.
#
9
2001, 42, 1073.
71%
380
Section 160
Coinpendiuin of Organic Synthetic Methods, Vol 11
HYDRIDES FROM ETHERS, EPOXIDES AND THIOETHERS
SECTION 159:
This section lists exainples of the reaction R-0-R'
5 eq Sin12,t-BuOH , 1 d
OB u Nakata, D.; Kusaka, C.; Tani, S.; OSiMe,
-
R-H.
*
PhH-HMP A
.
.
Tetruhcrlrnn Lett., 2001, 42, 415.
1 . "Cp2Zr" 2. D,O
*
80%
"Cp2Zr" = (Cp2ZICl2/2eq BuLi/THF, -78°C) Ganchegui, B.; Bertus, P.; Szvinoniak. J. Synlett, 2001, 123.
SECTION 160:
HYDRIDES FROM HALIDES AND SULFONATES
This section lists the reductions of halides and sulfonates, R-X
-
R-H.
cat Pd(OAc).L, 2 0 sec iniavw aves
>95%
Iones., Lockley, W.J.S.; Lu, S.-Y.;Thompson, S.P. Tetruhedron LEtt., 200Z, 42, 331. AcOH , HBr , aniline Br
Br
NH2
reflux, 4 h
Choi, H.; Chi. D.Y,J. Am. Cheni .Soc., 2001, 123, 9202.
70% NH,
Hydiides f m n IIalides
Section 160
38 1
Ni/C , Pph3 , K&03 M%NII=BII, ,7.5 h b s h u t z . B . L ; Tomioka, T.; Sato, K. Synlett, 2001, 970. InCI3 ,Bu3SnH , TIIP
PhCI1,Br
PhCII3 ,2h Inoue, K.; Sawada, A,; Shihata, I.; Baha. Tetruheclron Lett., 2001, 42, 4661. It
86%
1. BuLi, THF, -78°C 2. 9-(2H]-9-Ph-tluorene
-7X"CA rt
89%
mtrat.J.-C.; Pillon, F.; Rousseau, B. Tetruhedrnn h t t . , 2001, 42, 5001.
3% NiCIl(PPh3)2, 3% PPh3, 18 h M~NI-I*BH,,K2C03, M t C N , 40°C quant
Toinioka, T.; Pfeiffer, S.S. Tctrult~dronLett., 2001, 42, 7737.
;-
decaborane , 10%PdK:
*
A
94%
M t O I I , rt ,5 h Ph Ph Lee, S.H.; Jung, Y.J.; Cho, Y.J.; Yoon, C.-O.M.; Hwang, H.4.; yoon. Synth. Coiiriiiun., 2001, 31, 2251.
-
(2-f~171)3GeH,BEt3 ,TIIF, 1 h C12%-I Nakamura, T.; Yorimitsu, H.;Shinokubo, €1.; Oshirna. K. Brill. Cheiit. Soc. .Jpn., 2001, 74,747.
Ph
Br
Ni(R) ,TIIF, reflux , 12 h
t-
*
c121'25-H
4
Ph
w; Alvarez-Manzaneda, E.J.; Chahhoun, R.; Meneses, R.; Romera, J.L. Synlett, 2 0 0 1 , 485.
99%
89%
382
Section 160
Compendiuin of Organic Synthetic Methods, Vol 11
0r.i --
-
N-Hg
&C02Bn
i-Pr
011
-
Lr
3
5-
i-Pr
&C4Bn
93%
I Wang, Y.-C.; Ynn. T.-H, Chcm.Coimiun., 2000, 545. I n , H 2 0 , 8O"C, 3 h
*
>99%
0.01M sodium ddecylsulfate Ph Park, L.; Keum, G.; Kang, S.B.; Kim, K.S.; Kirn..Y. J. Chem. Soc.. Yerliin Truns. I , 2000, 4462. cat [Ni(OA~)~/Al(acac>3] , NaH 1
CXH17
TIIF, reflux , 15 inin, t-BuOH
n quant
Massicot, F.; Schneider, R.; Fort. Y.; Illy-Chexrey, S.; Tillement, 0. Tetmhedron, 2000, 56, 4165. N -i- Pr
N 4Pr
S d l z , MeOH ,It , 5 h
93% Aelteman, W.; Eeckhaut, A.; De Kimpe, N. Synlctt, 2000, 1283. 4
(M~o),P(o)II, 16 h
*
*
Br
Ph Br 4.5 NEt, , DMF ,70°C Ahhas, S.; Haves. C.J.; Worden, S. Tetrulicdron Lett., 2000, 41, 3215.
0-snBu2cI Br
Enholm.; Schulte n,
DMA , AIBN ,80"C NaBII4, 6.5 h J.P. 0r.g. Lett., 1999, 1, 1275.
M
Ph
93%
(2-fiuyl)3GeH , BEt,
' C12H25-H THF,lh Nakamura, T.; Yorimitsu, H.; Shinokuho, €I.; Qshima. K. Synletr, 2999, 1415. c12H2s-I
92%
67%
Section 162
IIydrides from Ketones
\ /
383
3 q i-PrMgBr ,TIIF, rt
c1
10% (C5H5hTiC12,2 d
93%
Hara, R.; Sato, K.; Sun, W.-H.; Takahashi. T. Chena. Conznzun., 1999, 845. Bu,hDII,, ‘I’HF ,r t , 5 inin P hCH,Br * PtlCH3 Ndrabimhan.; , . Swarnalakshmi, S.; Balakumar, R.; Velmuthi, S. Synth. Conmiin., Z999, 29, 685.
PdA4CM-41 , EtOH, H,
*
90%
0
43%
: Rahman, A.; Bandyopadhyay, T.; Haritha, Y. Synth. Conimun., Z999, 29,691.
SECTION 161: HYDRIDES FROM HYDRIDES NO ADDITIONAL EXAMPLES
SECTION 162: HYDRIDES FROM KETONES This section lists examples of the reaction KzC-(C=O)R
w
C o ( n ) , MI(^), 100°C , 1 4 h
-
RzC-II(R).
0+A+ CC”” CO2H
41% 13% 46% Sawatari, N.; Yokota, T.; Sakaguchi, S.; Ishii. Y. J. Org. Chern., 2 U U Z , 66, 7889.
2.5
0
.
; Lokot,
NaBH3CN, THF 2N aq 1I+
I.P.; Lakhvich, F.A. Synlctt, 2 U U Z , 1391.
0
384
Section 162
Compendium of Organic Synthetic Methods, Vol 11
A
Ph
H3POZ ,cat I 2
AcOIf ,reflux
n
* Ph
qumt
0
Hicks, L.D.; Han, J.K.; Frv. A.J. Tetruherlron Lett., 2000, 41, 7817.
Pt , K-10 , 5 0 har Hz
*
170°C. 15 h Tomk.;London, G . ; Bartbk, M. Synlett, 2000, 631.
cat R~C12(PPh3)3,PhH
*
t-BuOOH , 20°C
& 87%
Murahashi. S . 4 . ; Komiya, N . ; Oda, Y.; Kuwahara, T.; Naota, T. J . Org. Cherii., 2000, 65, 9186.
KMnO4 , CuS04.5
H20
DCM ,ultrasound, 3 h
-
Mdiarovh, M.; Toma. S.; IIeiihanovL, A. Tetrultedrnn, 2000, 56, 8561. Me2SiClII, 5% InCb
*
DCM , 2 Y C , 2 h Syrrlett, Z999, 182.
Ph Ph Miyai, T.; Ueba, M.;
1. N2H, ,toluene ,micmwavas 16 miI1 2. KOH , microwaves, 30 inin PhP h' Gadhwal, S.; Baruah. M.; ' I Synlett, 1999, 1573. ~
98%
Ph
Ph-Ph
70%
Ph
99%
95%
Section 165
3 85
Hy&-ides from Misc.
SECTION 163: HYDRIDES FROM NITRILES This section lists examples of the reaction, R-CEN .-+ R-H (includes reactions of isonitriles (R-NEC). NO ADDI'IIONAI, EXAMPLES
SECTION 164: HYDRIDES FROM ALKENES NO ADDITIONAL EXAMPLES
SECTION 165: HYDRIDES FROM MISCELLANEOUS COMPOUNDS
4-
Ph
S0,Ph
NI I Ph
Ph
Sin, AcOH, E O I I air ,rt , 1 h
0
Liu, Y.;
O r g . Prep, Procecd. Int., 2001, 33, 376.
L
2-
-yNHPh86% 0
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 12 PREPARATION OF KETONES
SECTION 166: KETONES FROM ALKYNES
q L Ph
Ph 15%50% Marchueta, I.; Verdaguer, X.; Moyano, A.; Pericbs. M.A.; Riera. A. Org. Lett., 2001, 3, 31.93.
SnC1, ,aq EtOH
Bosch.;Jefferies, L. Trtruheclron Lett., 2001, 42, 8141.
0
10% RuCp(MeCNXPF6, acetone 0 10% CSA, 1.3 € 1 2 0
02Me COZMe Trost. B.K;Brown, R.E.; Toste, F.D. J . Ant. Chenz. Soc., 2000, 122, 5877. MO2C
75%
Section 167
Ph
Ketones from Acids
=
ji
cat Tf2NI-I, H 2 0 ,dioxme
=
lOO"C, 2 d
Tsuchimoto, T.; Joya, T.;
Ph
387
Ph
; Kawakami, Y. Synlett, 2000, 1777.
1 . PhNHz , 1% CpzTiMe, 100°C , toluene
Ph
97%
2. S O , , D(3M
*
\
Haak, E.; Bytschkov, I.; Doye. S . A n p w . Cheiii. Int. Ed., 1999,38, 3389.
92% Ph
SECTION 167: KETONES FROM ACID DERIVATIVES 1. CDMT, NMM , THF, rt
2. EtMgX ,& I , 0°C
Ph
De Luca, L.;
'
Ph
Et
98%
-triazine CDMT= 2chloii~-4,6-d~iiethoxy-[1,3~] ; Pvrcheddu. A. 01%. Lett., 2001, 3, 1S1Y. graphite , 450°C , 7 6 0 m m
miauwaves (2x2 min)x6,450"C 90% E.J.; Chahboun, R.; Meneses, R.; Romera, J.L.
Barrero...; Alvarez-Manzaneda.
Synlett, 2001, 485.
MeMgBr , TIIF, 50°C
80%
r:
F
4%) when F is replaced with H
Zhane.; Terefenko, E.A.; Slavin, J. Tetruheclron Lett., 2001, 42, 2097. Nal3Ph4 , KF , acetone cat Pd(Pl'h,)2C1,, 9 inin * mic 1uwa ves
W ' 0 dn-.;Wci, B.; Iiu, Y.; Liu, Z.;Yang, Y . Sywrh.
BQ(-
Coiriiriiin.,
98% 2001, 31, 3885.
388
Coinpendiuin of Organic Synthetic Methods, Vol 11
Section 167
0
Inoue, K.; Shimizu, Y.; Shihata, I.; Baha.
99%
Synletl, 2001, 1659.
Ao1*
PhB(OI1)z , 3 % Pd(FG-aci), ,60"C
*
9% PCy3.2 NazCO3, 20 h disucciioyl anhydride Ghosh, K. Chrrrr. Corrirririn., 2001, 2084.
Ph
Qs&nLL;
U
Ph cathodJMtCN 65 % Sn cathoddMKN 0% Ueda, N. Bull. Chern. Snc. Jpn., 2001, 74, 755.
24% 78%
u;
1. Pd(PPh3)4 2. KOAc
.
90%
Ph hP'
lBu
*
74% Ph i Malladi, R.K.; Tejedor, D.; Kelley, S. Tetrultedrnn hrt., 2000, 41, 999. 3. B B u ~
Ph
)(
mesoporous silica FSM-16
= hv , hexane, i t , 12 h Ph Ph . Itoh, A.; Kodama, T.; Inagaki, S.; Org. LEtt., 2000, 2, 331. BzCI , Cat PdClz(dppf)
78%
*
78%
AgzO, KzCO,, 80°C Chen, 11.; Dene. M . - L Org. k t r . , 2UO0, 2, 1649. PhB(0II)z ,CSZCO~, tolut~e C1
I'h
S% Pd(PPh3)4, 100°C
Ah
Ph
.c
Jladdach. M.; McCarthy, J.R. Tetruhedrnn h t t . , I Y Y Y , 40, 3109
80%
Ketones from Alcohols
Section 168
389
80%
N.A,; Korolev, D.N. Tetruheron Lett., I Y Y Y , 40, 3057. M%SiSnBUg, 10% P(OEt), 110°C, 20 Inill C1 Geng, F.;
Bu '
'-.
S% [$(C3H5) PCICl]z
*
63%
Me 3 Si Tetruherlmn Ixtt., l Y Y Y , 40, 31 13.
Bu
PhOMe , 10 inin, reflux COZ 1-1
;-
,
,.
Enviiric at -EPIC
* M
L
C
.
)
\ /
Sadvaife, V.S. Synth. Coiirniun., l Y Y Y , 2Y, 2587.
SECTION 168: KETONES FROM ALCOHOLS AND THIOLS
1. (COXl)Z, DCM , DMSO -78"C, 90 Inill 2. NEt, ,-7X°C,2 h
ic,
3. "1 TIIF , --78"C + it
I ro
0
Fang.;Bandaruge, U.K.; Wang, T.; Schroeder, J.D.; Garvey, D.S. J . Org. Cheni., 2001, 66, 4019.
~ 69%
;
.
Section 168
Compendium of Organic Synthetic Methods, Vol 11
390
R~Cl2(PPh3)3,TEMPO, 0
2
1
*
98%
C6H13 100°C. PhCl ,7h C6Hl3 Dijksman, A.; Muino-Gonzilez, A.; Payerar, A.M.; Arends, I.W.C.E.; Sheldon. R.4. . I . Am. Chetn. Soc., 2001, 123, 6826.
x
(J
K 2 [ O ~ 2 ( O W 4 107 2 , 1 2 h
95%
t
arj t -B uOH
Ph Ph Diibler, C.; Mehltretter, G.M.; Sundenneier, U.; Eckert, M.; Militzer, 11.-C.;3eller. Tetruhcdron Lxtt., 2001, 42, 8447.
L .
S% V O ( X ~ K )MeCN ~,
*
80"C, 3 h
Ph
h.z
k , 98%
Ph
Maeda,Y.; Makiuchi, N.; Matsumura, S.; Nishimura, T.; ITelnura.. Tetruhedron Lett., 2001, 42, 8877.
ph-Y
C5H1
- phT
5% Fe(C0)S , hv (Pyrex)
OH
pentane, 2 h Cherkaoui, 11.; Soufiaoui, M.; Gr&. R. Tetruhedron, 2001, 57, 2379.
KM n0,-A120
Bi(N03)3 , 5 min
*
55%
81%
Synth. Comrnun., 2001, 31, 2691.
silica gel supported Jones reagent
DCM M.11.; Wiggin, C.J. Synth.
SiMe,
0'
Montmoiillonite
1.
93%
2o
hexane ,4h Ph Ph SiMq Patrocinio, A.F.; Moran. P.J.S. Synth. Coriirirun., 2001, 31, 2457
Samajdar, S.; Becker, F.F.; IhukJ!&
0
Coiiiriiiin.,
*
/J(
93%
2001, 31, 3383.
- A
PhI, 2% Pd(0Ac)z ,NaI-ICO, 0 1I
Bu,NCl , H 2 0 . 20 h
Ph
Zhao, M.;& M. -7&;Hu, R.-II.; Song, C.-S. Synrli. Conzrmn., 2001, 31, 3665.
87%
Section 168
Ketones from Alcohols
391
'Z
csw I
qcsH
[RuCh( PPh3)3/B uLi]
quant
TI-IF, 20 min ON 0 Uma, R.; Davies, M.K.; CsMsy, C.; Gs& & EUI:J. Org. Cirerrt.,2001, 3141.
1
liu(tmp)(O)2, M3E , 120°C
* 92% 10 atm N,O Ph Ph IIashimoto, K.; Kitaichi, Y.; Tanaka, H.;Ikeno, T.; Yamada, T. Chern. k i t . , 2001, 922.
&
Ph
Ph
1 . Fe(N03X.') H 2 0 , 100"C, 15inin
-
2. acetone, H,O
0
Zhao, Y.-W.; Wan!.
Y.-I,. J. Clietii. Res. (S), 2001, 70.
+Cn
Ph
95%
0
1. 1.1 a 1 P4-t-Bu. 'iliF/hexane 0°C -+ rt , overnight
Ph
Ph
2. p ~ buffer 7
PhS'
P4-C-Bu = t -BuN=P [-N= P( NMelX], Mamdani, H.T.; I-Iartlev. R.C. T~truhedrnnLcjrt., 2000, 41, 747.
58%
PhIO ,PPNO Ph
CiflII) s a k n catalyst
Ph - ..
hdam.;Gelalcha, F.G.; Saha-Miiller, C.R.; Stegmann, V.R. J. Org. Ch~ni., 2000, 65, 1915.
JdOI1
PhI(OAc), , DCM, 20"C, 5 h
*
CiflII)-salen C1 Adam, W.; Jlaira. S.;IIerderich, M.; Saha-Mijlles, C.R. Org. Lett., 2000, 2 , 2773.
10% N-hydsoxyphthalinkle , EtOAc 0.5% Co(OAc), , 5 % mcpha
Glr 13
70"C, 3 h
99%
90%
*
Iwahama, T.; Yoshino, Y.; Keitoku, T.; Sakaguchi, S.; Ishii, Y J. Org. Chern., 2000, G5, 6502.
Coinpendium of Organic Synthetic Methods, Vol 11
392
(,i
Al2O3,Br2-Alz03 ,DCM 1 ,
P
h
)$
*
Bi(NQhe 5 H 2 0 , Ac0I-I
Ph
4% Cu(OAc)2, HzO
0
83%
Ph
Love.;Nguyen, B.T. Synth. Cotilnzun., 2000, 30, 963.
Phh
Section 168
Ph 99%
0
Tymonko, S.A.; Nattier, B.A.; Mohan. R.S. Tetrulierlron Lett., ZYYY, 40, 7657.
,
-
B
U
Ph G 01.1
PhBr , 1% Pd2(dhah-CHCI3, 100°C 2% R-( +)-BINAP ,dioxane , KzC03
x
1% mcpha, 1% TEMPO
+
Jy
1% V0(OEt)Cl2, rt
Ph
0 2
, MeCN, 1.5 h
96%
92%
1% B u f l B r , CIIzClz,rt
C6II13 C6H13 pvchnovskv. S.D.; Vaidyanathan, R. J. Or#. Clwm., 1999, 64, 310
Ph
1
Ph
Nishimura, T.; IJernura. S,.I. AIJI.C h i . Snc., 1999, 121, 11010.
Ph
0
94%
0
K1TclhrlTd.; . , Ochiai, Y.;Takizawa, S.;Takahata, 14.; Neinoto. I
Chctit. Conirniin., I Y Y Y , 1387.
RuCI,(PPh3)3 , TEMPO 0 2
, 100°C , PhCl , 9 h
Dijksman, A; Arends, I.W.C.E.; &Idon.
/uu
Ph
Ph
t
C6H13
1
90%
Chern. Cornniun., 1999, 1591.
F~C13.6L I Z 0 , solid stale
90°C
Jy
* Ph
01.1 Zhou, Y.-M.; Ye, X.-R.; )<x
393
,acetone,2s"C
*
98%
I'h Ph Baumstark, A.L.; Kovac, F.; Vasquez, P.C. Can. J. Chin., 1999, 77, 308. 11202, Na2WO.4, 90°C, 4 h
77%
Me(C,NI7),N IISO, C3I-I7 Sato, K.; Aoki, M.; Takagi, J.; Zirnmerman, K.; pJovori. Bull. Cheni. Sor. Jpn., 1999, 72, 2287.
REVIEWS: "Selective Oxidation of Secondary Alcohols,"
Tctr-uhc.h-on, 2001, 57, 9765.
Related hlethods: Section 48 (Aldehydes from Alcohols and Phenols).
nph
SECTION 169: KETONES FROM ALDEHYDES
Phh
C
I
I
O
1. PhLi, TIIF 2. TMSCl
*
98%
Ph
Nudtlmdn.; , . Garcia, G.V. .J. Org. CIicrn., 2001, 66, 13x7. PhCI-10, BF3*OEt2 , CHzCl2
Ph It, I d Ph Chan, P.W.11.; Kamijo, S.; m a l n o t o . Y ,Synlett, 2001, 910.
P hC1I 0
C I I ~ X I I B US% , Rh(PPh3),CI
LBu
75%
20% 2-amnino-3-picoline , micmwaves ph 10 min Jun. C.-IL; Chung, J.-H.; Lee, D.-Y.; Loupv. &; Chatti, S . Tcri-uhedron Lett., 200Z, 42, 4803.
B uC1 I 0
, toluene , 80°C , cat (BzOk cat N-hydir,xyphthalirnide
4Lv BU
67% Tsujimoto, S.; Iwahama, T.; Sakaguchi, S.; Lshii. Y . Clierrt. Cornriiun., 2001, 2352.
Compendium of Organic Synthetic Methods, Vol 11
394
6
Section 170
C3H7CII0, SLCO~, PhH 5% t-B uOII , 2 d
C3H7 81%
0 OH 0 Pacut, R.; Griinm, M.L.; Kraus, G.A.; Tanko. J.M. Tetruhedron LL'tt., 2001, 42,1415. 1. 1IZNNI-ISO2Tl)l
P hCI-I0
2. PhCHO , EtOH , NaOEt 55°C , 2 d
Anele.;Neitzel, M.L. J. Org. Clzeni., 2000, 65,6458.
r";CTs
Ph
PhCHO
*
NLI+
aq THF, 50°C. 2 d
LB
42%
59%
8".
Ph wal. V.K.; de Vincente, J.; Pelotier, B.; IIolrnes, I.P.; Bonnert, R.V. Tetruhedron Lett., 2000, 41, 10327.
b
Xia, M.;
e
.
,
Ph2I' CI- , 5 % PdClz t
DMF ,2076 LiCl ,40"C, 3 h
Ho
89%
SyntA. Cnnrrrrun., 2000, 30,531.
c€10 Br
1. h-pr
, EtOH
5% Pd( O A C ) ~2, 2. 100"C, 1 d
KOAC 71x6896
. V,; Quan, L.G.; m o t o . Y , Tetrukedron Lxtt., 1999, 40,4089.
SECTION 170:
Pr
KETONES FROM ALKYLS, METHYLENES AND ARYLS
This section lists exainples of the reaction, R-CI-11-I495 nm) ,02,rt E- tetraphenylphoxphin
C€12C12,rt , 2.5 h
OH
*
82%
0
CusSv.;Belotti, D. Tetruheclron Lr.tt., 2001, 42, 4329. KMnO4/CuSO,-5 1120
~o
neat, 1.3h
Shaabani, A.; J-ee. D.G. Tetrd~erlronLett., 2001, 42, 5833
4
Ph
Ce(OTf), , MtCN ,r ~ t
/
- 1Ic: Ph
P I1
+ 15%
H20 9.5% 16.4%)1 1 2 0 99.7% L.d.rlll.; Herbert, M.; Cushnyr, B.; Bhatt, A.; Terrano, D. J. Chern. Soc.. Perkin Trans. 1, 2001, 578.
+
90%
2A.c5~4O (PhCNhPtC12 , DCM , 5 %AgShFs
85.7% -
%*
*
Furstner.;Voigtlinder, D.; Schrader, W.; Giehel, D.; Reetz, M.T. Org. Left., 2001, 3 , 417.
Taber.;Sethuraman, M.K. J . Org. Cl7c~in.,2000, 65, 254.
404
Compendiuni of Organic Synthetic Methods, Vol 11
R U , ( C O ~ ,cprz=crIz
C O , 2 0 a h , toluene 160°C. 20 h
Section 176
. ,
Ie, Y.; Chatani, N.; Ogo, 'I.; Marshall, D.R.; Fukuyama, T.; Kakiuchi, F.; J. Org. Chem., 2000, 65, 147.5.
BzCl, Ga(0Nfh
Ph
Nf = nonafluoiubutanesulfonate Matsuo, J.-i.; Odashima, K.;
0
Synlett, 2000, 403.
cis[ RuV'( 6,6'-Cl$py)~O~](C104)~ McCN ,it, Nz , 3 0 inin
Che. C . - N ; Cheng, K.-W.; Chan, M.C.W.; Lau, T.-C.; Mak, C.-K. J. Org. Chern., 21100, 65, 7006.
1. NaOCl , NaBr ,TBAH-HS04
LPh
* Ph
2. H20
Ph-Ph
86%
Clark, J.H.; Grigoropoulou, G.; Scott, K. Synth. Coninzun., 2000, 30, 3731.
M
e
\O /G
ACZO,Cat Sc(OTf), , 4 h MeN02,5O0C 89%
Kawada, A.; Mitainura, S.; Matsuo, J.-i.; Tsuchiya, T.; Bull. Cheleni. SOC.Jpn., 2000, 73, 2325. incpha ,N a H C Q ,air
CHzC12, rt
MitIz; Xia, C.; Tian, H. Tetrulicrlron Lett., I Y Y Y , 40, 8915.
88%
0
99%
-
Section 177
Ph
Shi, Q.-Z.;
Ph 1
405
Ketones froin Ketones
NaB1.4 , C L O ~ ,95"C, 1 d
aq dioxane Ph J.G.;Cai, K. Syntlt. Conunun., I Y Y Y , 29, 1177.
90%
1. Na , C3H7C02Me TIIF, 25°C
periasamv. M .; Keddy, M.R.; Bharathi, P. Synth. Corrinrun., ZYYY, 29, 677.
C103-Si02.140"C
t
Ph-Ph
a
5h Ph Bose. D.S,; Sunder, K.S. Synfh. Cornrnicn., J Y Y Y , 29, 4295.
CI-I~(CO2II)2, PPA, 2 h GO-80°C
-
92%
Renault, 0.;Dallemagne, I).; Pitult. S. Org. Prep. Proceed. Int., 1999, 31, 324.
SECTION 177: KETONES FROM KETONES
This section contains alkylations of ketones and protected ketones, ketone transpositions and annulations, ring expansions and ring openings and dimerizations. Conjugate reductions and Michael alkylations of enone are listed in Section 74 (Alkyls from Alkenes).
For the preparation of enatnines or iinines froin ketones, see Section 356 (Anline-Alkene). 1 . LDA , TIIF, -78°C , TI-IF 2.2.S%[Pd(1~3-C~IIs)CI12
7.5% his -f errwe ne- his-phosphine ligand , 3 h , allyl-0,COEt 90% (82% ee) You, S.-L.; JIou. X.-L.: Dai. I,.-X.; Zhu, X.-7,. Org. L , t t . , 2001, 3, 3149.
Section 177
Compendium of Organic Synthetic Methods, Vol 11
406
1. EtOK ,-78"C,2 5 h 2. cat BuLi , LiBr , HMPA -7XC , 12 h ,
pu
Yu, W.;
I
Tetrukedron Lett., 2001, 42, 369.
iMe
S -'3. _
Ph-02CCF3
cat I'd(
q3-GI 1s C H=CH CH2)(CF~COZ), * p&ph
'I'IIF, reflux
60%
Ohora, Y.; Ogawa, Y.; I~nni,Y.; Kawamura, T.; TSUJLX. J. Am. Clirrit. Soc., 2001, 123, 10489. OTMS
Ph
0
BF,.OEt,, CH2C12, -78°C ;-
85% (88:12 &ns:cis) Kimura, C.; Hosoya, 11.; Yunadoi, S.; Yokoe, I. Tetruhedron Lett., 2001, 42, 1095.
, 2 . 4BEt3
5% pd(OA~)z,10% PPh3 THF,rt,S h
Horino, Y.; Naito, M.; Kimura, M.; Tanakn, S.; W r u . Y, Tetruhedron Lett., 200Z, 42, 31 13.
;-
Bahu, S.A.; Gunnnathan, C. Synth. Corizmun., 2001, 31, 1205
A
NBu3 , dioxane ,5% RuCb-n IIzO
Ph 3 ~1 PPh3, 18O"C,40 h Cho. C.S.; Kim, B.T.; Lee, M.J.; Kim, T.-J.; Shim. S.C. Angew. Cheni. Int. Ed., 2001, 40, 9SX.
Ph
70%
Section 177
Ketones froin Ketones
407
1 . 0.1 chiral imide 2. 2,6-di-t-Bu-phenol
TIIF, -78°C Yanagisawa, A.; Watanahe, T.; Kikuchi,
>99% (90% ee)
T.;mote. U,J. Org.
Chem., 2000, 65, 2979.
1. T f 2 0 , 0"C, DCM
2
i- Pr
)(/
Ph
-
3. t-BuOK, DMSO
N
O
F 96~91%
v. A.R-; Zhang, S.; K u r ~1.; , Wang, M. Org. k t t . , 2001, 3, 2807.
6
P(t-Bu)3
ecl
, 1"/u I'd( OAc h
, 1.3 NaOt-Bu,
PI1
Fox, J.M.; IIuang, X.; Chieffi, A,;
\ 91% J. Am. Cliern. SOC.,2000, 122, 1360.
toluene, 8 0 T ,12 h *
"If c8
C,III7Br, 4N NaOI-I , 100°C calix(n)arene catalyst , 1 0 h
0
.. . Shlmlzu.; Suzuki, T.; Sasaki,
6
Ph
Y.; Nirai, C. Synlett, 2000, 1664.
2. 1. LDA 2 5 % Pd2(dba)3CIIC1,
ACO
*
Ph&+
17
Phh
86%
0
1111111111
0
(87
Braun. M.; Lnicher, F.; Meier, T.Angew. Client. Int. Ed., 2000, 39, 3494.
13)
Compendium of Organic Synthetic Methods, Vol 11
408
1
Section 177
A
1% Cu(xac), , 2.5 eqBujSnH
*
85%
PhH, reflux , 5 h C I-INz Ph Ph Tan, Z.; Qu, Z.; Chen, B.; Wanc. L Tetruhedron, 2000, 56, 7457.
&
C N ~ X H C ~ HAcOII, I ~ , 0, cat Mn(OAc)z, 80°C
C6H13
cat Co(0Ac)z
Ph Kawatsura, M.;
+.
Chenz. Conutzun., 2000, 2317.
Iwahama, T.; Sakaguchi, S.;
ji
85%
2% Pd(dba)2/ferrocenylphosphine ligand PhBr , NaOt-Bu, TEIF
*
2 5 T , rt
J. Am. Cl7crn. Snc., 1999, 121, 1473.
Ph
5 % child ligand , 2 eq LDA 2.5% [(q3 c3 I11,)PdCl],
MqSnCI ,30inin, DME -0AC
Trost.;Schrocder, G.M. .I. Am.
99% (86% ee) Clieiiz. SOL-., ZYY9, 121, 6759.
Amauld, T.; Barton, D.H.R.; Norinant, J.-F.; Doris.
. J, Synth.
Cnttzntun., 1999, 2Y, 117.
BJ. Org. Clwn., 1999, 64, 6915.
99%
Section 179
Ketones from Alkenes
409
Vdrmd.; . , Kumar, D. Synrh. Conunun., 1999, 29, 1333. Related Methods: Section 49 (Aldehydes from Aldehydes).
SECTION 178: KETONES FROM NITRILES
, cat sinIz
PhCN
t
cat NiI, , 30 inin, rt 11.-Y.; Song, S.-E. Totruhedron Lttt., 2000, 4 1 , 937. 1.
x/,
68%
Ph
mBr , 4 q Z n , 0.4 AICI, ?HI;, 2 h
2 . 2 M IICl
61%
U ,, S . - Y . ; Lin, L . 4 . Tctrulic*dr~in LLTtt., 2000, 41, 8803.
B
SECTION 179: KETONES FROM ALKENES
0, , McSO,II , act MLK"
10f%I'd(0Ac)z , lS% NPMoV/Cl 50°C , 6 11 NPMoV = ~~~Iybdovanadophosphate Kishi, A.; Higashino, T.; Soknguchi, S.; Tefrultcclmnk t t . , 2000, 41, 99.
A \
C 1 0 h1
i-PIOII
,S%j
P ~ ( O A C )20% ~ , Py
toluene , 0, ,60°C
Nishiniura, T.; Kakiuchi, N.; Onoue, T.; Ohe, K.; J. C h m . Soc., Porkin Trans. 1, 2000, 1915.
==? (XSn Bu3
*
A
1%
70%
ClOH21
phv
* JCozMe Bn,NBr, 'ITIF, reflux , 12 h 0
C02Me
Yasuda, M.; Ohigashi, N.; Shihata, I.; Balm & J . Org'. Chenz., 1999, 64, 2180.
>99%
410
Compendium of Organic Synthetic Methods, Vol 11
See also:
SECTION 180:
Section 180
Section 134 (Ethers from Alkt~es). Section 174 (Ketones from Ethers).
KETONES FROM MISCELLANEOUS COMPOUNDS
Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from Alkenes).
1. CH,=CIIOBu, a t dppp, NEt, 2.5% Pd(OAc)2, 100"C, 18 h
2. HCl
[bmin] BF4
ionic liquid medium Xu, L.; Chen, W.; Ross, J.; Xiao. J. Org, ,!.eft., 2001, 3 , 295.
MMPP = mgnesiurn inonopemxy phthalate Lee. K,; Im, J.-M. Tetruliedr-on Lett., 2001, 42, 1539. KMn04 , A1203, acetone
Jo
rt,2h
Chrisman, W.; Blankinship, M.J.; Taylor, B.;
m.C.H Tetruhedron Lett., 2001, 42,4775.
1. PhLi, THF, -78"C, 1 d
2. AcOH ,0°C 0 O2N Santos, R.P.; Lopes, R.S.C.; Lones. C..C. Synthesis, 2001, 845.
N-O€I
Nattier, B.A.; Eash, K.J.;
0.5 Bi(NO3h.5 HzO , xi acetone
72~95%
)(
0.1 C U ( O A C ~ * X H2~ hO , Ph Montoniorillonite K-10 * Synthesis, 2001, 1010.
88%
41 1
Ketones from Misc.
Section 180
fin
A.R.; Mallakpour, S.E.; Mohaniinadpoor-Baltork, I.; Khoee. S. Synrh. Coniniun., 2001, 31, 1187 Dour.
B(011)2
A c 2 0 , dioxane , seakd tube /
cat [Rh(CH,=CH2)Cl]2, D M E , 16 h b t . C.G ; Watlsworth, K.J. Clzerii. Cornrnun., 2001, 2316.
2
PhPb(OAc)3
CO, 5
NaOMe, CI-IC13
& /
68%
lph 4
5% P~l(dl1a)~-CIICl~ , MeCN , rt
*
70%
Ph J98%
chird diphosphite coinplex Ph N C' 100"C, 1 d ' . Tetruhedron Asyrnnz., 2000, 11, 845.
MLCN, MS 4A , 80°C Org. Lett., 2001, 3, 4209.
*
' m i , p Y ,c w 3 N 2 0 3 ,
. .. .. Ghll\LI.; Bakhtiari, K. Synrh. Cornnwn.,
-
94%
Ph-CN
M
e
microwaves
O
O
\ /
C
2001, 31, 1x03.
MLO,(CN) SO,NEt,
* P hCN 66% 2S"C, E M ,2h Jose, B.;Saulatha, M.S.; Pillai, P.M.; Puhpu-L Synth. Cotnniun., 2000, 30, 1509. P hCII=N-OII
feiric sulfate , R H ,reflux
t PhCN 3h P e s a i . D.G,; Swami, S.S.; Mahale, G.D. Synth. Coninlurr., 2000, 30, 1623.
PhCXI=N-OII
81%
hC13, M d N , flux, 1.5 h
* PhCN 98% Barinan, D.C.; Thakur, A.J.; Prajapati, D.; S ~ ~ J & 1 'L Clzern. A Lett., 2000, 11%. P hCI I=N-OH
A N--01I
Ph
SKI,
. I X M ,rt , 15 inin
0)
t
Ph-CN
Chaudhari, S.S.;w n c h i . K.G. Synth. Con~niun.,I Y Y 9 , ZY, 1741.
96%
N 64%
424
Compendium of Organic Synthetic Methods, Vol 11
PhCH=N-NMeZ
Oxone ,wet Al20, , 6 inin PhCN
minuwaves
Ramalinram.~.; Reddy, B.V.S.; Srinivas, R.; Yndav, J.S. Synth. PhCH=N-OH
Section 195
TiCb(OTf), sealed iuhe
Irannoor.~.; Zeynizadeh, B.Synth.
8 0 T , 10 h
-
78%
Commun., 2000, 30, 4507.
PhCN
90%
Cointirun., 1999, ZY, 2747.
EPZ-10, microwaves 68%
6 nun I
B -;P.
c1
c1
Sadavute, V.S.; Sahu, K.R.Synth. Cnritinun., 1999, 2Y, 3409.
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 14 PREPARATION OF ALKENES
SECTION 196: ALKENES FROM ALKYNES
J. Org. C ~ P I O2001, I . , 66, 3176.
Herz, H . G . ; Schatz, J.;
112 , Lindlar catalyst ,DMF diethylenetiiuninc , rt , 18 h
-
Campos, K R.; Cni, D.; Joumet, M.; Kowal, J.J.; Lursen, R.D.; Reider, P.J. J. Org. Chmi. 2001, 66, 3634.
94% (74:26 E:%)
Watanahe, 11.; Terao. J.: h i l i e .
N. 0r.y. I x t t . , 2001, 3, 1733.
93% Chatani, N.; h u e , H.; Morimoto, T.; Muto, T.;
J. 01.8. Chent., 2001, 66,4433.
426
Section 196
Compendium of Organic Synthetic Methods, Vol 11
,THF, rt Lr
HS iMezOSiMe2H t-Bu,P-Pt(DVDS) 2 eq Bu,NF ,rt 5% Pd(dba)z
Denmark.;Wang, Z. Org. Lett., 2001, 3, 1073.
-iSiMe,
5%JdpPFLC12, W E +
1.25 Prahharasuth, R.; Yan V
MqSiCHNz 83"C, 7 h
PMP-S
2 PhI ,574) P d ( 0 h ) z NaOAc, Bu~NCI,DMF
P-h
100°C , 1 d
Larock. R .C, ; Tian, Q. J. Org. Chenr., 2001, 66, 7372.
1. TBDPSCl , imidamle DMF, rt
-* 62%
OTBDPS
2.2% Pd~(dha)3*CHC13 ,AcOH OAc 23% PPh3 , toluene, reflux El-Sayed, E.; Anand, N.K.;
Et
=
Et
78%
w J. Vrg. Chern., 200Z, 66, 5256.
85%
OAc
Org'. Lett., 2001, 3, 3017.
Et+cqEt YCozEt
S% I Pd(0Ac)z
AgzCO3, MeCN 20°C , 3h . Kotora.; Matsumura, H.; Gao, G.;
Et Et Org. Lett., 2001, 3, 3467.
72%
Section 196
Alkenes from Alkyncs
427
10% W(CO)j*'INF ,THF 3 eq EtOzC
ph
H20
C4Et
CO,Et
. ., K.;Kusama, 13. Org. Lett., 2001, 3 , 3871. IWdSclWrl.Maeyania,
CqEt 99% (>95:5 exo:endo)
I
w
DME 'heat
0
65%
Ajamian, A,; Gleason. J.1,. Org. kn.,2001, 3, 4161. I
.C02Me
*(:If&
-m
6%Me,SiCl, Kl' 1 1 h cat TBAF, PMHS , ether l%PdC&(PPh,)2,1% Pd,(dha), 4%J(2-furyl),P , 37°C; Maleczka Jr.. R.E.; Gallagher, W.P. 01-8.Lett., 2001, 3, 4173. 6% Me3 S 11C1 WABr
1 %PdClz(PPh3h ~
,CW" (CIIZh 73 %
CbPh
1% Pdzdha3,4% (2-fuyl)3P * aq Na2C03 , PMIIS , ether Ph 90% 3 7 T , 15 h Gallagher, W.P.; Terstiege, I.; M&& a Jr.. J. Ant. Cheni. SOC.,2001, 123, 3194. 011
C,II~
=
Cd17
1 % KU catalyst, CII2C12
(EtO),SiII
-
Trc,st. B.M,; Ball, Z.T. J. Am. Clicwr. Soc., 2001, 123, 12726.
Si(OEt),
~ ~ 1 - 1 ~
Jb 99%
428
Section 196
Compendium of Organic Synthetic Methods, Vol 11
c6H13-
a t Pt(PPh3)4, 15 h
- GHh 77%
PhS fi toluene, flux PhS Ph Sugoh, K.; w vasu. H.; Sugae, T.; Ohtaka, A,; Takai, Y.; Tanaka, A.; Machino, C.; Kamhe. N.:Hurosawa. H. J. Am. Clwm. SOC., 2001, 123, 5108.
Mqsi
Me3Si
)
SiMe,
I
,ether, 5 h
1. &Br
2 q Ti( Oi-Pr).J2 i- PrMgBr - 1 5 " C d -40°C 2. €130'
Me$; Okamoto, S.; Suhhnraj, K.; Sato. F. J.
C3H7
=
Airi.
Clzeni. SOC., 2001, 123, 4857.
PhB(OH)2, xi dhxane
c3 137
h
3% K h ( i ~ ~ ) ( C z H 4 )dppb 2, 87% * C31J7 C3HF lOO"C, 3 h JIavashi. T.; Inoue, K.; Tankguchi, N.; Ogasawara, M. J. h i . Chern. SOC., 200Z, 123, 9918.
BUOII ,2%Pd(OAc)2 2.5%phosphine ligand toluene, 2.5 eq Cs2C03 Asao, N.; Shimada, T.; Shimada, T.;
Yalnalnotc3 . Y, J. Ant.
MqSiI , toluene -50°C
+
Clzerit. SOC.,2001, 12, 10899.
OMe +
OMe
10°C
82) 84% OMe (18 Takami, K.; Yorunitsu, H.; Shinokuho, H.; Mntsuhara, S.; Q s h i m a Synlett, 200Z, 293.
Section 196
Alkenes from Alkynes
429
HSiCI, ,20"C, 18 h
1% [P~CI(JC-C~I-IS)]~ PFFOMe
H
tBu,,,
a,si+L'==(
*
81% (72% e e , S) Vo-Tranh, G.; Boucard, V.; Sauriat-Dorizon, 14.; GuihB. F. Synlett, 2001, 37.
Me
Ackermann, L.; Bruneau, S . ; Pixneuf. P.H. Synlett, 2001, 397. Ph
MLCN , 130"C, 18 h
Ph,P (0 100) 95% (95 5) 90% Kazankova, M.A.; Efirnova, I.V.; Kochetkov, A N . ; Afanas'ev, V.V.; Beletskaya, I.P.; Dixneuf, P.H. Synlett, 2 0 0 1 , 497.
+ N i ( a ~ a c )(EtO),PH=O ~,
PI
58%
cI4
Prakash, 0.;Shiinna, V.; Butra, €1.; jl4oriarty. R.M. Tetruherlron LL".,2001, 42, 553.
5%JPhCII(0Meh TlClOd, CH2Ch
-5O"C, 2 h
-
I'hM %
Me quant Niimi, L.; Shiino. K.; Hiraoka, S.;yokoz awa. T. Tetraheriron Ixtt., 200I, 42, 1721.
-
-
1 . 10% Fe(acacb , 3 eq Bu1-i. To1
2. IN IICl
Hojo, M.; Murakami, Y.; Aihua, 11.: Sakuragi, R.; Baha, Y.; Angew. Chern. Int. Ed., 2001, 40,621.
Bu
n 97%
-
430
Compendium of Organic Synthetic Methods, Vol 11
Section 196
S% Gmhhs' catalyst l h , PhH
Smulik, J.A.;
Tetrah~~drori Lett., 2001, 42, 171.
HSiCI3, 20"C, 18 h 1% [PdCl(n-C3H~)]2
H Me
Han, J.W.; Tokunaga, N.; Ph
=
COZMe
81% (72% e e , S) ash i. T, J. Am. Clwni. SOC., 2001, 123, 12915.
m
112 , Pdpuinice , EtOH .r
CD2Me 96% Ph cat ethylenediarnine , 12min GlllttdddUTid.; * . . Liotta, L.F.; Noto, R.; Deganello, G . Tetruhedron Left., 2001, 42, 2015.
[Ti(Oi-Pr),/2 i-PrMgCl] ether, -50°C
.-, -20°C
*
80%
0Me Delas, C.; Urahe, H.; Sato. F, Tetwheriron Lett., 2001, 42, 4147.
L;arock.; Yue, D. T~mdiedronLett., 2001, 42, 6011. 5 % Pd(PPh3)4, I'HF, 2 h
F3C
PhZnCl ,0°C -+ rt
F3
*
Konno.; Tanikawa, M.; Ishihara, T.; Yamanaka, €I. Clzezent. Lett., 2000, 1360.
ph
77%
Section 196
Alkeiies from Alkynes
43 1
at Pd(OAc)z/PPh,
McONa , MeOH 25"C, 1 d
Ph OMe OMe M.-.I,; Wei, L.-M.; Lin, C.-F.; Leou, S.-P.; Wei, L.-L. Tetralzerlron, 2001, 57, 7839.
qPh 5% [Rh(diphos)Cl], , DCE AgShF6 , rt , 2 11
Cao, P.;
Angcw. Chenz. Int.
Ed.,2000, 39, 4104.
62% (96% ee)
t-Bu,CuLi-LiCN , PBu,
-xo"c
t-Bu
Krduse.; , . Purpura, M. A n g w . Chun. Int. Ed., 2000, 39, 4355.
92% (25:75 E:Z) Ph
/ph
10% PhI,PPh3,5 5% Pd(OAc), eij N ~ O Ap:C p /h
NEt, , D M F , X0"C , 2.5d Ph
Dvker.-; Bomwski, S.; Henkel,
Ph G.; Kellncr, A,; Dix, 1.; Jones, P.G.
Tetrcrhedron I x t t . , 2000, 41, X259.
53%
Coinpendiuin of Organic Synthetic Methods, Vol 11
432
y e
I
Section 196
Me
cat [Rh(bisphosphine)Cl]2 DCE,rt,lh
* PhO2S
Wang, B.; Cao, P.;
Tetruhedran Lett., 2000, 41, 8041.
10% PPh, , 2 h
2 eq ALOH , toluene 10 eq Et3SiI.I, S O T
t
(70% Qh. C.H.; Han, J.W.; Kim, J.S.;Um, S.Y.; Jung, N.H.; Jang, W.11.; Won. H.S. Tetruheriran Lett., 2000, 41, 8365.
73% (14:lE:Z)
Madine, J.W.; Wang, X.; m n h o e f e r . R . h Org. IAtt., 2001, 3, 385.
Fernindez-Kivas, C.; M h d e z , M.; E & i w m x n . & J. Am. Chein. Sac., 2000, 122, 1221.
433
Allcenes from Alkynes
Section 196
60 psi C I f 4 I I 2 , DCM, 22 h
\&hp
cat Clz(FCyzhRu=CHPh , rt
phk 78%
Smulik, J.A.; Diver.. ' ' J . Org. Chem., 2000, 65, 1788.
&lori. M.; Kitamura, T.; Sakaihara, N.; Sato, Y. Org. Lett., 2000, 2 , 543.
aP y
LDA ,TfIF , rt
[2°zh4e *
I
76% (94:6)
jlarada. T.; Fujiwara, T.; Iwazaki, K.; Oku, A. Org. Lett., 2000, 2 , 1855.
1 .Bu,SnII, PhIi, rellux syringe , AIBN pump
~
-
2. icflux, satd K F , r t , 2 h
s
~
,
M
41: 75%
0 $ha. C.-K ; Zhan, 2.-P.; Wang, F.-S. Org. Lett., 2000, 2 , 2011.
BrQE:
KO11 , toluene, 15 niin
-
( C ~ H I ~ ~ N*T J ~
Br Oku, M.; hral.;Katayarna, K.; ~ S y r t l c ~ t2000, f , 493.
Ph
H
e
434
Coinpendiuin of Organic Synthetic Methods, Vol 11
1 . 2 eqNsNC12, 2eq NsNHNa 10% CuOTf
Ph*C02Me
2. aq Na2S&
L Ph
*
Section 196
C
Q
M
e
i
x
N HNs 76% (20:1 anti:syn)
Li, G.; Wei, 11.-X.; Kim, S.H. Org. Lttt., 2000, 2, 2249.
-
1. f-BuLi ,-78°C r t , ether 2. CI-I,=CHPh (syringe pump)
\b
Et
ether, rt ,5 min 3. MeOII
*
PE Ph
61% (97:3 E:Z)
Wei, X.; Tavlor. R.J.K, Angew. Cheni. Int. Ed., 2000, 39, 409.
IIC&COZEt, 10% Pd(0Ac)Z TFA , E M , rt
4.5% ( U E = 2)
Jia, C.; Lu, W.; Oyamada, J.; Kitainura, T.; Matsuda, K.; Irie, M.; J. Am. Chenz. Snc., 2000, 122, 12.52.
2 eq NgHSiMe, ,dioxane
M -eP
* Me,Si
5% RuCl(cod)(CSM%), 60°C
4
SiMq
Ph 56% Le Paih, J.; Dhien, S.; Ozdemir, I.; Dixneuf. P.H. J. Am. Chern. Soc., 2000, 122, 7400.
Zhang, Q.; U
J
. Am. Cliem. Snc., 2000, 122, 7604
Section 196
Alkcnes from Alkynes
Chatani, N.; Inoue, H.; Ikeda,
GH13-f
435
‘I’.; Murei.S..Org. Chm., 2000, 65, 4913. OC02Me
MqSiCN ,576 Pd(PPh3),
DujLX-Tankguchi,
oi
(-=JI“
5-
TIIF, reflux , 1 h
NC 91% M.; Yasuda, T.; Kawamura, T.; Ohora, Y. Org. k t t . , 2000, 2, 2635.
Ph-
N
CO2Et
Pd(OAc), , ALOH , It
I1
&
C4Et
*
Lu, W.; Jia, C.; Kitamura, T.; b w n r i i . Y. Org. I z t t . , 2000, 2, 2027.
78%
Plla tTHF Cp*RuQ(cod) 60h , 80°C CO,Et* ; -$m & Q -$
.
Ac 0 Jordan, R.W.; Tam, W. Org. Lett., 2000, 2, 3031.
Ph
=
PhI, 5% Pd(OAc)2 10% PPh3, DMF
Ph 2
~ X NaOAc, J
100°C
Bu~NCI
.
X
1. B u S K l . KF PMI-IS cat TEAF ,‘Pd(PPh,),
TIIF, ink-rowaves 2. Pd(PI’h3)4 lnicl~waves
-
62%
Tian, Q.; h o c k . R.C., Orx. Lett., 2000, 2, 3329.
t-Bu
ACO
Ph
t-Bu
Maleczka Jr., K.E.; Lavis, J.M.; Clark, D.11.; Gallaagher, W.P. Org. L.ett., 2000, 2, 3655.
86%
436
Coinpendiuin of Organic Synthetic Methods, Vol 11
Section 196
Bn-Y SiMe,
Bn-
N
1. 1.5 y (qz-C&)-Ti(Oi-Pr)z
/
*
\:;:
80%
ether, -30°C
Urahe, H.; Nakajiinu, R.;
SiMe3
01-8.Lc.rt., 2000, 2 , 3481. ,SiMe3
54%
Sudo, T.; Asao, N.;
J. Org. Chern., 2000, 65, 8919. 5 % ~( ( I I ~ - C ~ H ~ ) P ~ C , 2Id] Z 10%dppf , toluene, 70°C
= - uB
Bu
.
58% Radhakrishnan, U.; Gevorgyan, V.; Y;Unjlllloto
e
S
i
M
e
3
Bu
Tetruhedron Lett., 2000, 41, 1971.
SiMq
, DCM, rt
Gr uhhs' ca tal ys t Stragies, R.; Voigtmann, U.;
*
69% (1.9:l E:Z)
Tetruhetlron Lett., 2000, 41, 5465.
1. Bu3SnH,AKBN, PhH 7.6mM
2. PITS, DCM
?!d 54%
COzEt
Robertson. J,; Lam, H.W.; Ahazi, S.; Roseblade, S.; Lusch, R.K. Tetruhedron, 2000, 56, 8959.
Section 196
Alkenes from Alkynes
P h =
6
437
0
85"C, 96 h
92% Kawakami, Y. Cheni. Commun., 2000, 1573.
Tsuchirnoto, T.; Maeda, T.;;-
=
wo
F O B 1 1 II2,30rnin
3% Pd/purnice
&
OI'BDMS
OTBDMS 90%cis Gruttadauria. M.; Noto, R . ; Deganello, G.; Liotta, 1.I. Trtruhedron Left., 1999, 40, 2857. 0.1 BuLi/O.l CI12(COzMe),=
'IFIF, reflux, 5 h
COzMe
86%
Et0 C02Me
Kitagawa, 0.;Suzuki, T.; Fujiwara, 1%; Fujita, M.; Taeuchi. T. Teteruherlron k t t . , 1999,40, 4585. EOZC Efy--
: ( F e , ) 2
*
E0,C 97% Sturla, S.J.; Kahlaoui, N.M.; J3uchwald. S.L. J. Am. Clzcm. Soc., 1999, 121, 1976.
P h = Fujiwara, N.;
0.6 eq (CM,=CIICI-Iz~Inz13
TI IF
*
>to. Y , J . Org. Clrcvrr. 1999, 64, 4095.
A
/
94%
43 8
Compendium of Organic Synthetic Methods, Vol 11
Section 196
SiMe, 0.5 EtAICI2 , CH2C12
* 69%
-78°C
J. Am. Chern. SOC.,1999, 121, 3797.
Asao, N.; Shimada, T.;
(>97
3) 97%
maps, E.; Schmid. W, J. Or-g. Cltcvn., 1999,64, 7537
-Rw"'
1. Cp,ZrEt,
-Ph
2.12
3. CUCl
Tdkdhashl.; . . . Shen, B.; Nakajima, K.; Xi, Z. J. Org. Chenz., 1999,64, 8706.
Cp*2YMe--THF,rt
64%
*
PhSiI-13,1 d
Molander. G.A.; Corrette, C.P. J . Org. C h w . , l y y y , 64, 9697. PhCBCH , [(~~aphth)Rh(cod)] BF, DCM , 15°C. 15 inin Paik, S.-J.; Son, S.U.; Chvna. Y.K.Org. Lett., 1999, 1, 2045.
B u,cULi*Lil, ether 90%(67:33 E:Z) PUrpUrd, M.;
Eue .I. Org. Chem., 1999,267.
BU
Section 198
Alkenes from Alcohols
COZEt
o
1. PPh3 E M ,
CO2Et
o
NHPh
L
Eto2c+
NHPh
2. PhH , re!lux 3. toluene , reflux
Yavari. L;Asghaii, S. Tetruhedron, 1999, 55, 11853.
de Marigorta, E.M. J.
;-
439
Chciii. Soc.,
92~53~43%
Perkin Truns. I, 1999, 889.
REVIEWS: "Metal-Mediated Carhometallation Of Alkynes And Alkenes Containing Adjacent Heteroatoms," A.G.; Forgione, P. Tctruhedrori, 2001, 57,5899.
SECTION 197: ALKENES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 198: ALKENES FROM ALCOHOLS AND THIOLS 1 . MeMgCl, 'ITIF, it, 10 h C
d
r
l
~
~
c
'
2. N iK, NE14C1
u; Shook, B.C. Tetr-ufierlron Lett., 2000, 41, 8847. Saito, S.; Nagahara, ;.'l
Synlett, 2001, 1690
71% (1:l E:Z)
440
Cornpendiuin of Organic Synthetic Methods, Vol 11
Ph,P=CI-ICO$t, DMSO
+
mCqEt
o-iodoxyknwic acid, 1.5 h P hCH, OH
Section 199
*
Ph
98%
Maiti, A,; Yadav. J.S.Synfh. Conintun., 2001, 31, 1499.
=/FC EtO2C
Ph,P=CHCO,Et M I I O ~DCM ,
Br Wei, X.; Tiaylor.
Br
U J. Orb. Chcin., 2000, 65, 616.
Schmitt, A.; &&3ig
70% (40:60 cis:fruns)
H. -IT. Eicr. J Org. Chein., 2000, 3893. Ph,P=CI.IO,Me, MnO, ,DCM .t
toluene ,rt , 4 h Blackhurn, L.; Wei, X.; LyhAiJL
Chern. Coniinun., IYY9, 1337.
80% (>99% JZ)
SECTION 199: ALKENES FROM ALDEHYDES CHPh
11
bJMe
Me / \ , p v y
Me
PhCHO ,THF, r t , 15 inin
*
E-selective
mPh
Ph
91%
Wang, Z.; Zhang, G.; Guzei, I.; Verkade. J.G. J. Orb. Chein., 21)0I, 66,3521.
YHO Bu,P=-/
OB n Harcken, C.;
C0,Me
DCM , toluene
*
Org. Left., 2001, 3 , 3591.
FCo OB r
78% (91 : 9 ErZ)
Section 199
Alkenes from Aldehydes
44 1
7’NSCH=N,, DCM
P hCI I 0 Dias, E.L.;
t
1-296 Rh catalyst ; White, P.S.
J. Ain. Cliein. Snr., 2001, 123, 2442.
InC&-Zn , MLCN , 8h 1cflux
FhCIIO
62% 1:3.7 ( E Z )
I’h -0TMs
e
l’hM +
P h d p h
Ph
(98 Barman, D.C.; Thakur, A.J.; Prajapati, D.; Sandhu. ,I S . Synlett, 2001, 515.
2)
93%
EtO,CCII,P(O)(OEt), , NEt3
PhCHO
b h&C02Et 8 Kbar . M&N . 1 d €Ias-Becker, S.; Bodmann, K.; Kreuder, R.; Santoni, G.; Rein, T.; Reiser. Q Synlett, 2001, 1395.
c:110
1. L.iCI12SiMe3 * M 2. Et,NCI , aq TIII:
c
O
q
\ /
85%
s
M
e
3
86% Kwan, M.L.; Yeung, C.W.; Breno, K L . ; poxsee. K.M. Tetrulzerlron k t t . , 2001, 42, 1411.
c
C I I o KIIMDS , toluene, rt
A.B.;
PhCtIO
pyrc)zs -onps\q\
onPS
(91
Berthelette, C . ; St.-Martin, D. Tetruherlrnn Lcjtt., 2001, 42, 5149. 1. MeN02, AcOII-NH~UAC 100”C, 3 h
mEt
*
Ph
2 . BEt,, Et20-1120 Liu, J.-T.; Yao. C.-F. Tetrulierlron Ixtt., 2001, 42, 6147
P hCI I 0
9 ) OTIPS 67%
M K O z E t , I’(KNCII2C€I2),N
*
i-BuCN , 40”C, 2 h Tmulicdron, 2001, 57, 8047. Kisanga, P.; D’Sa, B.; Verkade. .I.
79%
I > h m C 0 ” ‘ 96%
Coinpendiuin of Organic Synthetic Methods, Vol 11
442
LiOt-Bu ,hexane , Z " C , 1 h Petroski. RJ,;Weisleder, D. Synth. Coiiimun., 2001, 31, 89.
I
Section 199
93% (En=140)
CHz(C02Ilh ,EOAc ,35h
cHo
CH=CHCOzH
graphik , ultrasound, 43°C
u; Zang, 11.-J.; Fang, .I.-Y.; Li, 1.4.;
77% Li, T.-S. Syntli. Conrrizrtn., 2001, 32, 653.
10%PhCHO , 10%Sn(OTf)z DCM, 0°C , N iiiin
ph+
76%
Nokami.; Anthony, L.; Sumida, S.4. Clienr. Em. J., 2000, 6, 2909. [ (PhO~P(O)CII~COzEt, DBU
PhCfIO
N d , 2 HMPA , -7X"C, 2 h J -78°C
-z
0°C
*
PhC C 0 , E t
86% (93:7 Z E ) Ando. K.; Oishi, T.; Hirama, M.; Ohno, H.; Ihuka, T. J. Org. Chern., 2000, 65, 4745. AlC13-Zn ,M&N ,ixflux PhCIIO
10 h
*
92% (99:l E:Z)
Dutta, D.K.; m a r . D, Tetruli~~rlron Lttt., 2000, 41, 6227. PhCIIO, KIIMDS ,THF I ~ C I D W L I -7X"C, -6, 1h OCH,CF3 OCHZCF3 Yu, W.; Su, M.; Ph-Crro
Tetruhedron ,!,eft., 1999, 40, 6725.
CHI3 , cat CrC13(thf), Zn , Me3SiCl , dioxane 25°C ,4h
Takal.;Ichiguchi, T.; Hikasa, S. Synlctt, 1999, 1268.
95% (100% z)
phw I
84% (955 E Z )
Section 201
443
Alkenes froin Amides
TMG = N,N,",N-tetranethylgmnidium
/
OZN
~ A . G . MCramp, . ; S.M.; Roherts, R.S.; Zecri, F.J. 01-8.Lett., 1999,1, 579.
Related Methods: Section 207 (Alkenes from Ketones).
SECTION 200:
ALKENES FROM ALKYLS, METHYLENES AND ARYLS
This section contains dehydrogenations to fonn alkenes and unsaturated ketones, esters and amides. It also includes the conversion of aromatic rings to alkenes. Reduction of aryls to dienes is found in Section 377 (Alkene-Alkene). IIydrogenation of aryls to alkanes and dehydrogenaticlns to forni aryls are included in Section 74 (Alkyls from Alkenes).
1. LDA lTMSCl 2. NBS , -78°C 3. TBAF , -78°C
TMS Dumeunier, R.;
-
OB n Tetrukrrlron Ixtt., 2000, 41, 10219.
SECTION 201: ALKENES FROM AMIDES Related Methods:
Section 65 (Alkyls from Alkyls). Section 74 (Alkyls from Alkenes).
NO ADDITIONAL EXAMPLES
OBn
Section 203
Coinpendium of Organic Synthetic Methods, Vol 11
444
jY
T6r
SECTION 202: ALKENES FROM AMINES BnO
hi-N
CHZ=CIIMgBr, THF BnO GOT,3h
-
N-AZi Bi'
Azi = 2-phenyl N-aziiidinyl group Kim.; Ohi, D.1-I.; Yoon, 1.-Y.; Cheong, J.H. J . Aiiz. Cl?Ci?t.SOC., 1999, 121, 5330.
89% Lee, K.; Kim, Y.H. Synrh. Conmun., I Y 9 9 , 29, 1241
SECTION 203: ALKENES FROM ESTERS
EtCu(CNXMgCI), 0°C Ito, M.; Murugesh, M.G.;
83%
4%
5%
EtMgCllcat CUCN, -18C 86% ' Tetruhedron Letr., 2001, 42, 423.
0 gh I
0
\
= toluene, heat
FaurC-Tromeur, M.; Zard. S.Z. T~~tr-ulzr~~Iron Lett., 1999, 40, 1305.
*
98%
445
Alke~iesfrom Ethers
Section 204
OMe
id
)$
10% Mo(CO),(ECN)~M e o ~ 15% c h i d bis-ainkle
0
*
NaII, CHz(C0zMe)z TIIF, 70°C
COzMe
; m /
(5
94%1W
Glorius, F.; E&T-A 01-8. .!At., 1 9 Y Y , 1, 141.
SECTION 204:
0
ALKENES FROM ETHERS, EPOXIDES AND THIOETHERS
(MezN)2P(O)Cl, IizO lSO"C, 30 inin
-
92%
Tetruherlron, 2001, 57, 227
Rlehi.;Bovicelli, P.; Sperandio, A. Zctrultcr/r.on,2000, 56, 1731.
p, N
I
I
Boc
1. NCS ,CCI, ,reflux , 3 h 2. mcpba , r t , 18 h
t
66%
D.L; Beck, E.X. J. Org. Clwnr., 2000, 65,8367
6.9'
COzEt
LiI ,.4mherlyst-15 , acetone rt,(lh
CSJIll
Antonioletti, R.; Bovicelli, P.; Fazzolari, E.;
* /
CSH11
80%
Zetruhedron k t t . , 2000,41,9315.
Compendium of Organic Synthetic Methods, Vol I1
446
Co salen complex 10 eq Na(IIg)
quant (NMR exp)
THF , 6 h Tetruhcdron Lett., 1999,40, 8747.
Isohe, H.;
Section 205
Jacoh, J.; m e n s o n . J K Cllerrl. Corllrlrun., 1999, 1003.
SECTION 205:
ALKENES FROM HALIDES AND SULFONATES
&j C02Me
I
I-C02Me
,MrCNPd(OAc)z, C ~ 2 c O 3IEflUX , tn-2-biylphosphine norhornene
62%
m e n s . M.,; Pacpin, J.-F.; Piguel, S.; Dahlmann, M. J. Org. Chem., 2002, 66, 8127.
Bu
SiMe3
1. ~
X C ~ SS Sd
2 , TIIF, I E ~ ~ U X
2.0.1 M aq HCl c1 m c e l l b n . J.M.; Bernad, P.L.; Bardales, E. Org. Lett., 2001, 3, 937. I
u M : s %
Pd(dhil)3*CIIa3
(CIl2=CHk h C l 1.5% P(2furyl)3 TIIF/H20 Ixtlux, 3h Takami, K.; Yorknitsu, 13.; Shinohulo, H.; Matsuhwa, S.; Org. Lett., 2001, 3 , 1907.
+
%: : =
c:dBr 1.
PPh2
PhCHO , toluene, 150°C 2. aq K2C02, 125"C, 51nin Westman. J. Org. LLtt., 2001, 3. DMF, 3, 3745. lXO"C, Smin
96% (>98% z)
Section 205
-
447
Alkeiies from Halides
p1 =q3= 5% CIIQ3, r t , 1 d
Bao, M.; Nakamura, H.; -()to.
80%
*
407;PPh, Y, J. Am. Clwni. So(-., 2001, 123, 759. CiCb-LiAlII, , CPrOII
M
* Ph TrrF, DMF 97.5% Oinoto, M.; Kato.; Sogon, T.; Mori, A. Tetrulrcdron Lett., 2001, 42, 939. C1
Ph
,OBn
Ar
CII2=CIISnBu3 , 2 eq KF
5% Pd(T'Ph,)4, toluene 110°C. 30 inin Synlrtt. 2001, 1557.
Ph
Chant..;I s e , M.;
90%
* Ph
Br C02H
NEt, , DMF ,I ~ ~ C I X ) W ~ V ~ X ~
Ph
95% (>99:1Z : E )
Br
P h / y 30 st?c Br Kuang, C.; Senboku, 11.; Tokuda. M Tetrulzerlvon D r t . , 2001, 42, 3803.
HMPA, 100°C
rBrB
100 torr
c
'
W
D
r
78% Van Veidhuizen, J.J.; Vos, T.J.; Zhao, P. Synth. Cornnzun., 2001, 31, 1367.
H;-
To11 IN
K/\ Br
hv , MeOH ,30 inin
-
PPh
TolIJN
0
Ph
75%
Aruna, S.; Kalyanakumar, R.; Ramakrishnan. V . T . Synth. Coritnricn., 2001, 31, 3125.
IIMPA , 160°C , N2, 15 inin ) .
Br
IlMSff
Khurdnd.; . . B:insal, G.; Chauhan, S. Bull.
mPh
Ph
93% (97:3E:Z)
Chmi. Soc. Jpn., 2001, 74, 1089.
Coinpendiuin of Organic Synthetic Methods, Vol 11
448
Section 205
MqSiCII=N2 , C€ICI3 2.5% Pd,(dha):,CHC& 15% AsPh3, i-PrNEt2 rcflux , 12 h
MeOZC Greenman, K.L.; Carter, D.S.; Van V
Br
Ph
0
Claphain, B.;
*
f l 6 %
Meozc
Tetruherlron, 2001, 57, 5219.
CHZ=CHSld3u3 , 2 % Pd,(dha), 20% t1i-2-fuiylphosphine , NMP
-Ax-
6 S T , 16 h
Ph
0
Ph
98%
J. O r g . Clwm., 2001, 66, 9033. Et
$1:
CpzZr
FA
Ph+cl
,
50°C. 12h , TIIF 2.5 DMPU, 2 eq CuCl
c1
63 %
*
Et
Ph +Et
Et
Duan, 2.; Sun, W.-H.; Liiu, Y.; Takahashi. T. Tetr-uhedronLett., 2000, 41, 7471.
Ulerstiuk.; Roy, C.D. Tetrulichm Lttt., 2001, 42, 325.5.
L
Ph
a
Fe ,MeOII ,reflux, 30 min
-
* Ph
ph
Br Thakur, A.J.; Boruah, A.; Baruah, B.; Sandhu. J .S. Syntlz. Coinntiin., 2000, 30, 157. DAI3CO. Br,NCl
Jefferv. 1'.Tctruherlmn Lctt., 2000, 41, 8445.
90%
Section 206
449
Alkenes from I-Iydiides
L€%
mPh
Sm/TIIF , TMSCl (trace H 2 0 )
Ph
5h
Br
Xu,X.; Lu, P.;
' i r
.
LZ. 1
*
82%
Ph
Y. Syntlz. Corrmrtn., 2UU0, 30, 1917. Me2C=C€IMgBr,20°C 3%)L~,c~c& ,TIIF
4 tr]NMP G.; Chaboche, C.; JCzCquel. M. Tetruhedrnn, 2000, 56, 2733
Ct-I2=CI-ISnBu3, I t 5 % ~Pd(PPh3)4, DMF 10%)CuI, A r
/N+
Barchin, B.M.; Valeiiciario, J.; Cuadro, A.M.; Alvarez-Builla, J.; Org. k t t . , I Y Y Y , 1, S45.
/ Vaouero...J. I
CH2=CI-ISllBU3 ,80"C l.S%J Pdz(dba)3, 6% P(t-Bu)3 2 . 2 ~ CsF 1 , dioxane , 12 h
87%
Littke, A.F.; Fu. G . C : . A n p w . Cherii. Int. Ed., I Y Y Y , 3 S , 2411
83%
Br Kim, M I . ; Wei, H.-X.; Willis, S.;
4
C02Et
C02E t
I . Br-Br
Syntlz. Corriniun., ZYYY, 29, 4179. , NaII, DMF
2. DBU ,75-XOoC
sa2 a2Et
Dunce.;Bums, S.E. 0 r - g . Prcp. Proceed Int., 1999, 31, 99.
SECTION 206: ALKENES FROM HYDRIDES For conversions of methylcnes to alkenes (RCH2R' 200 (Alkenes from Alkyls).
RR'C=C€I2), see Section
70x5276
450
Compcndium of Organic Synthetic Methods, Vol 11
Section 207
NO ADDITIONAL EXAMPLES
SECTION 207: ALKENES FROM KETONES
89% (56:44E:Z) J. Org. Chern., 2001, 66, 2990.
Rele, S.; Talukdar, S.; Banerji, A.;
1. BuCnCOLi, -78", THF
H 87%
2. IF, I'hH, reilux
E 1 O l C p C H O
1. LDA ,
P0(0&)2
*
81%
2. Ac@ 3. NaH
OAc
l(raus. G.A.; Jones, C. Synktt, 2001, 703. Copt
1 . Li , Naphth ,-78°C , 0 5 h 2. 0°C , 30 nun 3. henzophenone , rt
* Bu)(:"H
Shlndo.;Koretsune, R.; Yokota, W.; Itoh, K.; Shishido, K. Tetruherlron k t t . , 2001, 42, 8357.
A
1. EtS02Ph, BuLi
Ph
-L
2. Na(IIg) Bu 3.5% HMPA, Sm12 TIIF, 0°C , I h Mrllk6.; .. Murphy, F.; Kumps, L.; Ales, A.; Touillaux, R.; -; S . Tetruherlron. 2001, 57, 2609.
Bu
89%
86~69%
Carhallares, S . ; Dolan,
Alkenes from Nitriles
Section 208
-m 45 1
1 1 . 2 eq BuLi , ether, --78"C, 1 h C3H7 2. ~yclohexanone,-78°C , 3 0 mill
GH7
I
C3H7 75%
GH7
u; Song, Q.; Chen, J.; Gum, 11.; Li, P. Angew. Cliein. Int. Ed., 2001, 40, 1913. 1. K I I ,TIIF, 0°C , t-BuSiMe,Cl 2. 3.3 eq LDA , THF ,0°C
Ph+
3 . 3 . 5 e q TMSCl Ph
pk ,,,urSiMg
*
Ph
84%
SiMe3
bl&riL; Di-iring, M.; Seyferth, D.; Giirls, I-I. Chein. E w . J., 2001, 8, 573.
58% (89:11 , E:Z) Takeda. T.; Takagi, Y.; Saeki, N.: Fujiwara, T. Tetruhedron Lett., 2000, 41, 8377.
Related Methods: Section 199 (Alkenes from Aldehydes).
SECTION 208: ALKENES FROM NITRILES Br
Ph
CN
'111-, XI xTHF
-
*+p
Ph
X
69%I X=Me 73% Yoo. B . - K ; Lee, S . 4 . ; Choi, K.-1-1.;Keuin, S.-K.;KO, .[.-.I.; Choi, K.-I.; Kim, J.-H. Tetrulierlrnn I x t t . , 2001, 42, 7287.
X=II
Compendium of Organic Synthetic Methods, Vol 11
45 2
#
-0
1.5 eq CII2=CHMgBr, 1 h 1.6 CXIAgBF, ,-78°C
+
Section 209
0°C
Ph Agami,C.; Coutv. F,; l h n o , G. Org. Lett., 2000, 2, 2085.
91%
Ph
SECTION 209: ALKENES FROM ALKENES 2%[ Rh(cod)Cl], 8% TPPDS
P
h
A
-
PhB(OII)?_, Na2C03 phase transfer agent , H 2 0
mPh 80%
Ph
TPPDS= p h ( P
Lautens.;Roy, A.; Fukuoka, K.; Fagnou, K.; Martin-Matute, B. J . Ain. Chent. Soc., 2001, 123, 5358.
'OBr PI1
, 140"C, NaOAc
\ /
Pd-NaY zeolite, DMAC
89% trum (telle. P, Syrrth. Cormnun., ZYYY, 2Y, 1201.
o
88% m
Compendium of Organic Synthetic Methods, Vol 11
480
2eq PhH
-
SOCl2, TfOM, 1 d
0
II
PhHS\
Olah.;Marina, E.R.;
Section 224
Synlett, 1999, 1397.
92%
Ph
EtOAc ,rcflux 82% NO+-lXciuwn-6 NO2 W N 4 12 Irannoor. N. : Firouzahadi. 1-1.; Heydari, R. Synrh. Crunnrun.,I Y 9 Y , 29, 3295. N 0, 70%)€12SOdSi02,H N 0 3
E M , 2S"C, 1 d
78%
Smith, A.C.; Narvaez, L.D.; Akins, B.G.; Langford, M.M.; Gary, T.; Geisleer, V.J.;
Synrh. Conimun., I 9 9 Y , 2Y, 4187.
AcONOZ-Clay
-cues.
FEt \ /
96% (44153 o:p) J.A.E;; Filho, A.P.O.; Moran, P.J.S. Synth. Conrnaun., 1999, 29, 2169.
*
SECTION 222: OXIDES FROM KETONES NO ADDITIONAL EXAMPLES
SECTION 223: OXIDES FROM NITRILES NO ADDITIONAL EXAMPLES
SECTION 224: OXIDES FROM ALKENES
v C 6 F I l 3
Nd-12P02,MeOH, r t
0
*
H,II
BEt, , 2 h Na 0/-'C,jH13 DeprGle, S.; Montchainn. J.-L. J. Org. Chnt., 2001, 66, 6745.
80%
Section 225
48 1
Oxides from M i x .
ENO, , Amherlyst A
-C02Me
inicmwaves , 7 inin
COzMe
..
Bdlllnl.; Bosica, G.; Fiorini, D. Tetruhedron Lett., 2001, 42, 8471.
SECTION 225:
85%
OXIDES FROM MISCELLANEOUS COMPOUNDS
IISllllllll ..
0
D’
2. 1. EtMgX n-decylMgX , TIIF,THF ,-30°C
0
II
Dsy;;l c
0-inenhyl
Br
Br
89% (>98%ee ,S)
Capozzi, M.A.M.; Cardellicchio, C.; Naso. F.; Spina, (3.; Tortorella, P. J. Org. Chem., 2001, 66, 5933.
PPh, ,DEAD PhI-I, rt , 2 h
c
0 1I
82%
MJL; Weiler, L. Oq.Lc,lt., 2001. 3, 643. 0
0
PhNH3-
II
P-
I’hI, 2% Pd(PPh3)4
I-I,
3 “1 NEt3 , MtCN
JVlontchamp. J.-I,.; Dumond, Y.R. J. Aiii.
\ /
CIwiii.
II
* Ph-
P- 0- NH3+ ‘H
Soc., 2001, 123, 510.
L’M
e
0
-
9
~
10%)In(OTf), , 120°C
88% (38:62 0 : p ) Frost. C.G.; IIartley, J.P.; Whittle, A.J. Synlett, 2 U U Z , 830.
97%
482
Coinpendiuin of Organic Synthetic Methods, Vol 11
M 2.4KeqNBr, ,2% , 3H20 0 min OS03- PyrH'
p
Section 225
h
A
t
41%
A g N 0 3 , 0°C
Steinrnann, J.E.; Phillips, J.11.; Sanders, W.J.; 0
II
Org. LRtt., 2001, 3. 3557. 0
1. BBr3 , toluene-hexane
I
-30°C-
II
-70°C
Et / p\ 0 E t 2.MeOH, 20°C OEt Synthesis, 2001, 553. Gaovry, N.; 0
11/
95%
Et+oI1 OH 0
II
-P\
0 C 31-17
Ph$+ BF4-, DMF
*
ph/
II
P-OC3H7
a t Pd(PPh3)4 , KzC03 90"C, 3 h Zhou, T.; Chen. %.-C. Synth. Coniinun., 2001, 31, 3289. 0
c,I-17
0
!
\
0
SOCl2, DCM b
/sSms -78°Crt Ph
Schwan., Strickler, R.R.;
98%
OGH7
!
90%
Dunn-Dufault, R.; Brillon, D. Eur. J. Org. Chem., 2001, 1643.
NH4N03 , TFAA , MtCN PhB( Olih PhNO2 78% Salzhrunn, S.; Simon, J.; Surva P m s h . Q . K ... PLtrlsis. > . . N.A... Olrlh. * Q.kSynlett, 2000, 1485. R
PhMgBr , 5 h
Cardellicchio, C.; Fracchiolla, G.; Naso.; Tortorella, P.; Holody, W.; -hie Tetruhedron I z t t . , 1999, 40, 5773. n
Guzman, A.; Alfaro, R.; Diaz, E. Synth. Conzrnun., 1999, 29, 2967.
:w'
Comvendium of Orpanic Svnthetic Method8 “
V
Michael B. Srnitk Copyright 0 2003 by John Wiley & Sons, Inc
CHAPTER 16 PREPARATION OF DIFUNCTIONAL COMPOUNDS
-
SECTION 300: ALKYNE ALKYNE
Ph
=
TIPS
6 CU(OAC), TBAF,4h ) P h P yle ther
= =
Ph
68% Hueft, M.A.; Collins, S.K,; Yap, G.P.A.; Fallis, A.G. Org. Lett., 2001, 3, 2883.
Dai. W.-M; Wu, A. Tetrahedron Lett., 2001, 42, 81 %HI7
-
CuClz, KF/AlZ0, rniaowaves , 2 min
-
c8rI,, -
Kahalka. G.W.; Wang, L.; Pagni, R.M. Synlett, 2001, 108.
CpJr
3
-
C,H, 7
61%
1. CUCl
2. Bn-Br
,~ O O C 6 h,
Bn Liu, Y.; Xi, C.; Hara, R.; Nakajima, K.; Yamazaki, A.; Kotora, M.; J. Org. Chetn., 2000, 65, 6951.
-
36%
Compendium of Organic Synthetic Methods, Vol 11
484
=
Ph
SiMe,
C u a ,DMF ,60°C
-
Section 301
= =
Ph 6h Nishihara, Y.; Ikegashira, K.; Hirahayashi, K.; Ando, J.-i.; Mori.;Hiyama, T. J. Org. Chem., 2000, 65, 1780. 2.5% Pd2(dhah , 15% TFP 20% CuI, 2.5 eq TEA
P
h
T
B Br
'
* P h DMF , 8 0 T
Ph >99%
= =
Ph
71%
TFP = trk- (2-fury1)phosphine
&m. W,; Thomas, S.A. Org. Lett., 2000, 2, 2857. Si(i-Pr)3 BuLi ,hexane -78°C- 4 0 ° C B( r
70%
(i-Pr),Si Si( CPr), Eisler, S.; Tykwinski, R.R. J. Am. Chem. SOC., 2000, 122, 10736. CuC12, NaOAc, 3 h
-L-
P
supercritical C 0 2 Xi, J.;
P
P
h
quant
Chem. Commun., ZY99, 2369.
REVIEWS: "Acetylenic Coupling: A Powerful Tool In Molecular Construction," Siemsen, P.; Livingston, R.C.; Diederich. F. Angcw. Chem. Int. Ed., 2000, 3Y, 2632.
SECTION 301: ALKYNE - ACID DERIVATIVES
Koster, F.; Dinhus, E.; Duiiach, E. Eur. J. Org. Chem., 200Z, 2507
Section 302
485
Alkyne - Alcohol
yS”B::pc€40 -$
SECTION 302: ALKYNE - ALCOHOL, THIOL
TMS
TMS +$e
ML
OMe
TMS
(97 Savall, B.M.; Powell, N.A.; Boush. W.R. Org. Lett., 2001, 3, 3057.
, toluene, 60°C
TMs()-+
‘’W
22% Ho
3) 96%
= + , 5 0 % NEt,
OTMS
N Me2
20% Zn(0Tfh , 5 h
77% (98-%ee)
Anand, N.K.; Carreira.E.M. J . Am. Chem. Soc., 2001, 123, 9687.
Et02C--CI I 0
1. Me’s> Me
C=CII,
p --
w t Sc complex 2. KZCO,, EtOII
95% (98% ee)
Cvanb.; . . . Sweeney, Z.K.; Kovis. T.; Tedron, J.S. J. Am. Chem. SOC., 2001, 123, 12095. 1. CpzTiClz ,Mg ,TIIT; 2. PhCHO 3 . 1 0 % €ICI Yang, F.; &o.
G .: D
U Tetruhederon k t t . , 2001, 42, 2839.
72%
PhC-CII , ZnMez, toluene
CHO
10%chirdl amino-alcohol
Lu, G.; Li, X.; Zhou, Z.; k. W.L.. C t
,
b A S .C Tetrahedron Asyrnm., 2001, 12, 2147.
486
Compendium of Organic Synthetic Methods, Vol 11
Section 302
re-LGADH ( a reductase)
Schubert, T.; Hummel, W.; Kula, M.-R.;
x
92% ee Eur, J. Org. Chem., 2001, 4181.
HCCH , toluene ,Zn(OTf), N-Meephedrine , i-PrzNEt , 7 d* 79(:8%e)
CHO
Sasaki, H.; Boyall, D.; Carreira.
E.& Helv.Chim. Actu, 2001, 84, 964.
acetone , t-BuOK , 2 0 min
P h =
solvent free amoto. H,; Yasaka, S.; Tanaka, K. Bull. Chent. Soc. Jpn., 2001, 74, 185. P h O C H ,toluene, 23°C Zn(0Tf)L , NEt,, 2 h
I-PKHO
-iP&
(+)-N-methylephedrine
95% (90% ee) J. Am. Chem. SOC.,2000, 122, 1806. Frantz, D.E.; Flssler, R.;m e i r a . E .M,
Ph
2" alcohol dehydrogenase from Therinunueobucter ethanolicus Iieiss, C.; M l i ps. R.S, J. Chem. Sor., Perkin Trans. 1, 2000, 2821.
30% (60% ee, S)
, toluene, 23°C
H O( - =
(-)-N-methylephedrine , NEt, Zn(OTf)L Boyall, D.; L6pez, F.; Sasaki, H.; Frantz, D.;
C,H,7
-
1
5-nonanone , 4 eq SmI,
Org. Lett., 2000, 2, 4233.
*
c,H,~+.OH
BU
THF 84% Bu . . Kunlshlma.;Nakata, D.; Tanaka, S.; Hioki, K.; Tani, S. Tetruhedron, 2000, 56, 9927.
487
Alkyne - Aldehyde
Section 303
PhCmCLi , toluene, 1% M q G a -78°C ,0.1 h
BnO
Ooi, T.; Morikawa, J.; Ichikawa, H.; Maruoka.
BnO
P h G C H ,&Me2, 10%chiral amino alchol
PhCHO
90%
y Tefrclhedron Lerr., 1999,40, 5881.
toluene/TIIF , -20°C
* F% ,H -) ph
Nb 70% (68% ee, S)
u; Upadhyay, V.; Decamp, A.E.; DiMichele, L.; Reider, P.J. Synthesis, Z999, 1457. S d z , Pd(PPh,), , TIW
9
*
87%
Bn Bn Aurrecoechea. J.N; Fafianjs, R.; Arrate, M.; Gorgojo, J.M.; Aurrekoetxea, N. . I . Org. Chent., 1999,44, 1893.
1. (CyhB€I ,O"C + rt
*
62%
2.MeOH, 1 h
C3Ph " Ph Mahrwald.; Quint, S . Tetruhedrnn, 2000, 56, 7463.
-
1. COZ(CO)8 , cH*c12 ,rt /OH
2' HO*CSH,l
C5H11
70%
3. BF,*OEt,, -20°C 4. CAN , acetone, 0°C Diaz, D.D.; Martin. V.S. Tetruhedron Lett., 2000, 41, 9993.
Oxone, H 2 0 , MeCN-DMM KzCO3, AcOH , 3 h Wang, Z.-X.; Cao, G.-A.; Shi. Y . J . Org. Chern., 1999, 64, 7646.
6
SECTION 308: ALKYNE - HALIDE
/
NMe,
1. PPh,, CHI3, f-BuOK
~
2. t-BuOK, -78°C
mhel. P.: Rossat. 4Tetruhedrnn Lelt., 1999, 40, 8579.
6
-
I
/ 80~80% NMe,
-
Alkyne - Ketone
Section 309
49 1
e- ,NaI ,MeOH
w
C
p
h
=
x
88%
. . Nlshleuchi.;Kanahe, 0.;Itoh, K.; Maekawa, H. Synlett, 2000, 89. Br
II
CuI,MeCN, 1 d
*
40°C
11
+
Ph
- -
Ph
28%
SECTION 309: ALKYNE - KETONE
C3H7
=
TBHP , 0 2 ,70"C, 1 d
C3H7
CUCl2*2 H 2 0
U;Fong, W.M.; Chao, L.C.F.; Fung, S.1I.C.; Williams, I.D.
0
74%
J. Org. Chem., 2001, 66, 4087.
p h Y / OH
[Cp+RuCl( acetone ,pzMekRuCp*Cl] N H p 4 * ph$
78%
rellux, 4h 0
Cp*=NsCcjM~j Nishihayashi, Y.; Wakiji, I.; Ishii, Y . ; J. Am. Chem. SOC., 2001, 123, 3393.
I
1 . 4 eq t-BuLi ,-78°C 2 . C 0 , - 7 8 " C , 1h
I
3 . 2 tq PhCIIzBr, 1 h -78°C rt
. .
*
+
Song, Q.; Hen, J.; Jin, X.; XLZ; J. Am. Clieni. SOC., 2001, 123, 10419.
65%
-
Section 309
Compendium of Organic Synthetic Methods, Vol 11
492
=
Ph
()-SeCOMe cu
* 98% ee) Aladm, F.J.; Guerra, F.M.; Moreno-Dorado, F.J.; Bustamante, J.M.; Jorge, Z.D.; Massanet. W Tetruhedron Lett., 2000, 41, 3200.
496
Section 3 15
Compendium of Organic Synthetic Methods, Vol 11
CO/N2D2 (200/800/100 psi) THF , H 2 0 , Pd-C ,CuCI,
-CO2€I
18 h
OH
(22% 24%) 59% conversion Shen, C.; Garcia-Zayas, E.A.; Sen. A. J. Am. Chent. SOC.,2000, 122, 4029. 1 . 2 q L D A , THF, -78°C 2. L i , 5% DIBB , t-BuCHO , -78°C
*
C1-C02H
t-Bu Pastro, I.M.;
COzH
52%
Tctrulzedron Lett., 2000, 41, 5335.
-
SECTION 314: CARBOXYLIC ACID ALDEHYDE N O ADDITIONAL EXAMPLES
SECTION 315: CARBOXYLIC ACID - AMIDE
iiL
t- Bu / \ N
1.
Ph
Borg, G.; Chino, M.;
toluene ,0°C 2. cat RuCb=H20,N d 0 4 CH2C12, M&N/I-120
*
t-BU/s\N
O2
Illman. J . A , Tetruhedrnn Lett., 2001, 42,
0
x
Me *Ph H
CQZH
8 0 ~ 6 2 %(99: 1 dr) 1433.
60 eq co , 120°C , PdK:
I
N - m thylpyrmlidine 98% L B r , 1% If,SO, 11 * acetainide Beller. M.; Moradi, W.A.; Eckert, M.; Neumann, 11. Tctrulzedron Lett., 1999, 40, 4523.
CHO
MeCN
1. HZSO4, € 1 2 0
M :1-0e
2. M e 0 0.25% PdBr2/2 PPh3
Beller.;Eckert, M.; Moratli, W.A. Synbtt, 1999, 108.
/ \
76%
Section 317
Acid - Ester
497
-
SECTION 316: CARBOXYLIC ACID AMINE
#
-0
Buillus meguteriuni PYR 2910 KHCO3 ,N H ~ O A C1, h
CO,H N K phosphate buffer (pH 7) H suprcritical CO, 59% MJtsuda.; . . Ohaishi, Y.; Harada, T.; Yanagihxa, R.; Nagasawa, T.; Nakmura, K. Chern. Conunun., 2 0 0 1 , 2194. N
Ir
KEVIE WS: "Recent Developments in Catalytic Asymmetric Strecker-Type Reactions," Angew. Chem. In?. Ed., 2001, 40, 875. Related Methods:
Section 315 (Carhoxylic Acid - h i d e ) . Section 344 ( h i d e - Ester). Section 351 (Anine - Ester).
SECTION 317: CARROXYLIC ACID - ESTER 1 . aq NaOH , TIIF , 0°C
70%
2. IIBO+ J. Org. Cheni., 2000, 65,5834.
4:
(DIIQI))zAQN, Me011 , ether
0
Chen, Y.; l i a n , S.-K.;
I1O2c(CI I 3 C 0 , I I
99% (95% ee)
J . Am. Chern. Soc., 2000, 122, 9542.
€ICOzBu+ctme, D O W ~50WX2 X i
70"C, 3 h
;-
. . '
I
.
aCOzMe
-30°C
I IO,rA CH d,CO,B u
95% Ishii, Y.; Fujisaki, S. J. Clieni. SOC., Pcrkin Truns. 1, 1999, 3023
Section 322
Compendium of Organic Synthetic Methods, Vol 11
498
CARBOXYLIC ACID - ETHER, EPOXIDE, THIOETHER
SECTION 318:
NO ADDITIONAL EXAMPLES
SECTION 319: CARBOXYLIC ACID - HALIDE, SULFONATE NO ADDITIONAL EXAMPLES
-
SECTION 320: CARBOXYLIC ACID KETONE Cu(OAck-H20, air, 90°C Ph
3% aq AcOH:MeOH
NO2
Nikalje, M.D.; Ali, I..; Dewkar, G.K.;
.
61%
phC ' 02H
Tetruhedron L.ett., 2000, 41, 959.
Also via: Section 360 (Ketone - Ester).
SECTION 321: CARBOXYLIC ACID - NITRILE NO ADDITIONAL EXAMPLES Also via: Section 361 (Nitrile - Ester).
-
SECTION 322: CARBOXYLIC ACID ALKENE OTMS
1. PhCIIO
Me$i
dOTMS
2. NHdCI Lensen, N.; Mouelhi, S.;
P hCHO
, DMF , KOH, rt 96% Synth. Coniniun., 200Z, 31, 1007.
CH2(C02112,Bentonite microwaves, 5 min
=
phL(m2H 79%
Loupy, A.; Song, S.-.I.; Sohn, S.-M.; Lee, Y.-M.; &von. T.W, J. Chem. Soc., Pcrkin Truns, 1, 200Z, 1220.
m2H
Section 322
1.
499
H2N*~d N H ,rt , 5 h
2. Ph(h4e)CIBr 3. H30'
Me
-
Acid - Alkene
62% (57:43 RR:RS)
Brun, E.M.; Gil, S.; Parra. M, Tetruhedron A.synzrii., 2001, 12, 915.
1.1 atmCO, 2 DMU Ni(cod)z ,TIIF, 0°C
" \
2 . 2 eq PhZnCl 2h , 0°C
Takimoto, M.; Shimizu, K.; MmJl. PhCHO
B
'
Org. Lett., 200Z, 3, 3345.
~
69%~
Ph
CHz(COzH), , S O , , 4 min
83%
t PhCH=C HC02H mimwaves Kamar.;Reddy, B.V.S.; Reddy, P.T.; Srinivas, D.; Yadav, J.S. Org. Prep. Proceed. Int. 2000, 32, 81.
89% Zhu, S.; Pardi, S.;
0 Tetmhedron Lett., 2000, 41, 9589. EtZnBr , 5 % PdCl,( MeCN)L
*
/Iccog
I DMF ,25"C, 12 h Ct Aharhri, M.; Parvain, .I.-L.; Kitamura, M.; Noyori, R.; Duchsne, A. J. Org. Chein., 2000, 65, 7475.
90%
1. ClCH=CHCl , hv 2. 25% Z n , toluene 85~80%
3. A c ~ O 85°C , 0
Gauvry, N.; Coinoy, C.; Lescop, C.; Iluet. F, Synthesis, 1999, 574. CHz(COZH), , piperidine
0
* PhCH=CHCO,H quant micmw aves , 15 sec P e l l h , R.F.; Mamposo, T.; Gonzrilez, E.; Calderh, 0. Synth. Coinmun., 2000, 30, 3769. PhCI 1 0
~
Coinpendium of Organic Synthetic Methods, Vol 11
500
P h =
1 atm C@ ,Ni(cod),
t
2 eqDBU, 0°C
US.; Nakagawa, S.; Koizumi, T.; Hirayama, K.; -to.
J. Org. Chem., 1999, 64, 3975.
32% aq MeC03H
&OH
AcOII ,0°C , 3 d
Section 323
1 0
85%
ZH
Y,
H
H o 2 b 0 2 H
+
(5
2) 70%
e. A.B. Synth. Conznzun., 1999, 29, 1463.
PhCHO
CHZ(CO2II), , Py/Pip , 2 min
* PhCII=CHCO,H inimwaves De, A.; Karchaudhuri, N. Synth. Conrntcm., ZYY9, 29, 573.
97%
u; Also via:
Section 313 (Alcohol - Carboxylic Acids). Section 349 (Amide - Alkene). Section 362 (Ester - Alkene). Section 376 (Nitrile - Alkene).
SECTION 323: ALCOHOL, THIOL - ALCOHOL, THIOL ASYMMETRIC DIOLS
/a/
I . 5% microencapsulated OsO, 5% (DHQD)zPIIAL, 30°C
Ph
-
H \LMe
Ph+
Hb/
K3Fe(CN)6,aq acetone, K 2 C 4 2. K,Fe(CN)6, K2C03,2OoC
OH
HO
85% (78% ee) ibhavashi. S,; Ishida, T.; Akiyama, R. Org. Lett., 2001, 3, 2649.
&Ph Ph
1 . 5 H 2 0 2 , 2 q TEAA 2% O s 0 4 , 5 % flavin
(DHQD)zPHAL ,0°C r-BuOHIH,O
Jonsson, S.Y.;
Adolfsson.H.; Biickvall,
Lr
$P,h
Ph
OH
89% (90%ee) J.-E. Org. Lett., 2001, 3, 3463.
Alcohol - Alcohol
Section 323
J==
501
BnSePh, K 2 0 ~ 0 2 ( 0 H ) 4 KzCO3 , (DHQD)$'HAI-, iy t-BuOII , 1 d
Me
( y l : ph
Krief.; Castillo-Colaux, C. Synlett, 2001, 501.
-
RR-oli gomer-salen catalyst H,O ,MeCN/DCM ,THF NMP ,100"C
96% (97% ee)
98% (94%ee)
"O,,
J. Ant. Chem. Soc., 2U01, 1 2 3 , 2719.
Ready, J.M.;
Mehltretter, G.M.; DGhler, C.; Sundermeier, U.; &&,rJ&
Tctruhedron Lett., 2000, 41, 8083.
60% (>20:1 dr; >99% ee)
Notz, W.; J.ist. B, J. Am. Chcm. Sor., 2000, 122, 7386. KzOs02(OIl)4 , (DHQD)zPHAL
PhSe(O)Bn, KZCO, ,
p>
t-BuOOII*
%
-'t7 011
Knef.;Colaux-Castillo, C. Tetruhedron Lett., l Y Y Y , 40, 4189.
K6.
Ph
cat Ru(chiral his lunine)
DMF,HCOOII/NEt3 1 d ,30-60"C
z
96%(97%ee)
qPh OH
Ph
OH quant (90.4:9.6d1:nwso) 9 9 % ee , RR Murata, K.; Okano, K.; Miyagi, M.: Iwane, I*.; Noyori, R.; Ikariya, T. Org. Lett., 1999, 1, 1119. 0
Section 323
Compendium of Organic Synthetic Methods, Vol 11
502
NON-ASYMMETRIC DIOLS
PhCHO
3 eq S m , 2 M HCYTHF
20T, 1d
% +
Ph 80% (4852 dl-meso)
01I
Talukdar, S.; Fano .I.-J.& 01-g. Chem., 2001, 66, 330.
lltiit~t
CpzTi(Ph)CI ,Zn ,Me3SiC1
THF (0.05M) ,rt
*
O
O
OH
H
60% (99: 1 b-ms:cis) Yamamoto, Y.; Hattori, R.; Miwa, T.; Nakagai, Y.-i.; Kuhota, T.; Yamamoto, C.; Okamoto, Y.; I&&, J. Org. Chem., 2001, 66, 3865.
Barrero.;Cuerva, J.M.; Herrador, M.M.; Valdivia, M.V. J. Org. Chem., 2001, 66, 4074. Ph
ph-cIm
,TtIF
*
1% Zn-linked BINOL ,-30°C
OH 94%
Kumagai, N.; Matsunaga, S.; Yoshikawa, N.; Ohshima, T.; Org. b t t . , 2001, 3, 1539.
0.1%K 2 0 a 4 , Cinchona alkaloid in ordered inorganic support
W C O Z f i
Ph
Motorina, I.;
K,Fe(CN), , K2C03 ,t-BuOWH20
.
Org. L.ett., 2001, 3, 2325.
(89 : 1 syn:antQ 9 2 % ~89%ee
j j C o +
Ph
OH
54% conversion
503
Alcohol - Alcohol
Section 323
p
10%Ti complex 3 eq Mn , 2 5 T
PhCHO
.-
15 eqTMS CI MeCN
&Ph
Ph
--6H
94%(96:4 d1:meso)
Bensari, A,; Renaud, J.-L.;Riant. 0, Org. k t t . , 2001, 3, 3863.
Bu
cat 0 ~ 0 4a, t NMM 2% TEAA
Jonsson, S.Y.; FZrnegCdh, K.; lhddlJ& -
PhCHO
~
catflavin
Bu+
B~
95%
OH J . Ant. Chern. Snc., 2001, 123, 1365.
1.3%Ce(Oi-Pr), , Mn TMSCl
-
2 . 2 N HCl 0 1I
CJroth.U.;Jeske, M. Synlett, 2001,
(80
129.
chiral Ru complex , HC0,H NEt3, CI12C12, S O T , 6 h 0
o
97:3)
GIlesheck.;Heckroth, 11.; Schmickler, H. Tetmhedron Lc:tt., 1999, 40, 3137.
C02Me
1.2 TsNNaCl , aq MeCN
c
1% KZOSO,(OH)~
Pringle, W.;
HOiiiiiiii
Hoiiiiiiii
NH Ts
12) 88% bothrac
(88
Sharnless.K.B. .. Tetrahedron L.ett., 1999, 40, 5151. 1. 1 . 5 q IDA ,TIIF, -78°C 2 1 . 5 q MoOPD, -78°C
0
Hara, 0.;Takizwa, J.-i.; Yamatake, T.; Makino, K.; Hemada. Tetruhedron Lett., 1999, 40, 7787.
% Bz
OH
1. TFAA , 11-IF 2. heat, NEt, 3. 2.5MNaOH
*
Y,
UoH N
I
Bz
Cossv. .I,Dumas, ; C.; Pardo. D .G,Eur. J. 01-8. Claem., 1999, 1693.
63 %
Section 326
Alcohol - Amine
515
SECTION 326: ALCOHOL, THIOL - AMINE NIBu
l.LDA,THF 2. PhCHO ,-78°C
QH
NHBu
QH
3. NaBH4, THF/MeOH
Pb
Veenstra.; Kinderman, S.S. Synlett, 2UOZ, 1109.
Nv
1. X 1 4 , PhH, reflux
Ph
Uucawa.
56% (synhnti = 2.4)
OH
2.10% HCl
PhI
r x
NHz
70%
Y,;Tsuji, C.; Miyazawa, E.; Sakamoto, T. Tetruhecfron Lett., 2001, 42, 2337. PhNMe, , hv , 1 d
PhCHO
* Ph'
Kim.;Mah, Y.J.; Kim, A.R. Tetrahedron Lett., 200Z, 42, 8315.
OH
cIIo 1. BrZnCH,COg-Bu T H F , O 0 C , 2 h vi-Bu I
NBnz
2.aqNH4Cl
.
AndrBs, J.M.;
Ph-
79%
OH
+
c0i-B~
NB n,
NBn, (78 22) 69% ; PBrez, A.; PBrez-Encaho, A. Tetrulzedron, 200Z, 57, 8521.
BnNtI, , LiC104
a
&p
a
m
MeCN ,reflux
95%
u ; VBzquez, V.; m r o . 1. ; Juaristi, E. Synth. Commun., 2001, 31, 3295
'OZEt
1. MeCOzEt ,MgN(i-Prh ether, 0°C
CN
2. MgN(i-Pr),
Nakalshima, T.; Mano, M.; Morikawa, 0.;Konishi, H. Chem. k t t . , 200Z, 602.
516
Section 326
Compendium of Organic Synthetic Methods, Vol 11
a-Zr(03PMe) 2(03PC6H4S03H)0.8 PhNHz, neat, 40°C , 2 0 h
Cunnl.;Epifano, F.; Marcotullio, M.C.; Rosati, 0. Eur. J. Org. Chem., 2001, 4149. .
I
MeLi , ether, -90°C 64%
OH
I
Bn
Band.; Huher, F.A.M.; Tveremvsky, V.V.; Bolesov, I.G. Tetruhedron, 2001, 57, 1593.
Do
PhNHz , CeCI3-7 H20-Nd
D
b
O
DCM,rt
75%
H "0,
, 831. Reddy, L.R.; Reddy, M.A.; Bhanumathi, N.; ~ S y n t h e s i s2001,
NHPh
P hNHZ ,H 2 0 p-cyclodextrin
Reddy, L.R.; Reddy, M.A.; Bhanumathi, N.;
*
D
H
82%
"'N H&
m Synlett, 2000, 339.
8 atm 112 , t-BuOK, i-PrOH ,rt ,4h
NMq
O
L,
RuC12(diphosphine) 1,2-diamine)complex
L
N
M
%
99% (92%ee) Ohkuma, T.; Ishii, D.; Takeno, H.; povori. R. J. Am. Cltem. SOC.,2000, 122, 6510. Ph
/
Pi
85% (90:lO E : Z , 97:3 er) Whisler, M.C.; Vaillancourt, L.; Beak. P. Org, Lett., 2000, 2, 2655.
Section 326
Alcohol - Amine
517
0"
1.1 eq PhN€12,reflux, 4 h
*
hexafluom-2-propano1
'"% NHfi
84%
Das, U.; Crousse, B.; Kesavan, V.; Bonnet-Delpon, D.; BCgue, J.P. J. Org. Chem., 2000, 65, 6749.
Charrada, B.; Hedhli, A,; Baklouti.
PhCI 1zN-P h
4Tetruhcdron k t t . , 2000, 41, 7347.
henzophenone , TiC14, Sin
*
57%
Ph
I
TIIF, 60°C , 3 h Ma, Y.;T h a w . Y.Org. Prep. Proceed. Int., 2000, 32, 567. 1.2.2eq S d 2 , 1% NX2, THF 2. i-PrN=CHPh * 3. 1130+
>'u.
80%
a!-
Machrouhi, F.; &my. J -1 .. Tetruhedron Lett., 1999, 40, 13 15.
NI14011 , inicrowaves
82%
Ph
NHi-Pr
%11
77%
8 min
hdstr6m.U.M.: Olofsson. B .: Sornfai. P. Tetrahedron Lett., 1999, 40, 9273.
90%
Done.:Fang, X.; Schroeder, J.D.; Garvey,
D.S. Synthesis, 1999, 1106.
PhNHz, Sn(OTf), ,ether
*
94% % ",,
Sekar, G.;
m.V.Y. J. Org. Cheni., 1999, 64, 287.
518
Compendium of Organic Synthetic Methods, Vol 11
Section 327
- %d r HQ
Bu,SnH ,AZBN ,PhH KflUX
NHOMe
54%
I
COzBn
COzBn
Naito.; Nakagawa, K.; Nakamura, T.; Kasei, A.; Ninomiya, I.; Kiguchi, T.
J. Org. Chem., 1999, 64, 2003.
-
SECTION 327: ALCOHOL, THIOL ESTER
Et
MesLi,THF -78”C, 1 h
. Kondo._Y.;
0
70% Asai, M.; Miura, T.; Uchiyama, M.; Sakamoto, T. Org. Zxtt., 2001, 3, 13.
@I(0H)OTs p-To1 Ahe, S.; Sakuratani, K.;
*
L p-Tol J. Org. Chun., 2001, 66, 6174.
CHC13 , =flux
O
T
S
67%
cat NIIPi , PhCN , 7 5 T cat Co(acach , 14 h Hara, T.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Clzenz., 2001, 66, 6425. 1. CIIZ=CHCOzMe, 75% Py-box 2.5% [ ( c ~ d ) I r C l ],~E t S i H , 25°C
\/“Io 5
6 Bn
2. H30+
OBn 50% (>95:5 syn:anti) Zhao, C.-X.; Duffey, M.O.; Taylor, S.J.; Morken. J.P, Org. k t t . , 2001, 3, 1829.
Section 327
Alcohol - Ester
LDA ,EtOAc, TIIF
PhCHO
519
-I% COzEt
Ph IIuerta, F.F.; BLckvall, J.-E. Org. Lett., 2001, 3, 1209.
>99%
1. CbMeSiH , 2 . 7 DuPhos 1.25% [RhCl(C02)]2 d C l z M e
A
2. PhCHO, -46°C 3. H30+
Zhao, C.-X.; Bass, J.; Morken. ,I.P. Org. Lea., 2001, 3, 2839. 1. In,TIIF, 0°C + rt 2. PhCI10,O"C , 4 h
OAc
Br
94% (>60: 1 syn:untQ
0 Ac
ardo. M.; Girotti, R.; Morganti, S . ; TroInhjni.
Lai,
86% (85:15 syn:unti)
c. Org. k t t . , 2001, 3, 2981.
1) 85%
(20
s.;
I
; Jasinski, J.P.; Reid, S.N.; Staples, R.J. Org. k t t . , 2001, 3, 4169.
/\ljsph
PhCIIO ,TiCh*NBu,
* P
0
h
V
S
P
h
u Matusrnoto, ; N.; Funakoshi, S . ; Manta, N. Synlett, 2001, 1959.
99% (86:14 yn:unti)
2
i-l'KIiO , 10%Me3A1 CHzc12, I t , 22 h
Smpura. I.; Nevalainen, V. Tetruhedron La., 2001, 42, 3905.
80%
Compendium of Organic Syii thetic Methods, Vol 11
520
Section 327
-2% HCl,(thf), ,toluene 16 h
OH
4) 79% R = adillnantyl (95 R ' Ishihara, K.; Nakayama, M.; Ohara, S.; Yamainoto. I I . Synlett, 2001, 1117. OTMS
PhCHO
-
QH -
yMe
*OMe
chiral Zr catalyst, toluene 94% (78% ee) C;II,OH ,0°C K o h a v a s L L ; IrAani, H.; Yamashita, Y.; Ueno, h ; Shimizu, H. Tetruhedron, 2001, 57, 8 1. 0 2 Ci -Pr PhCHO
i-PrCHO , 2% Y50(Oi-Pr),,
13% salen ligand ,DCM , MS 4,4
Ph
Ph Mascarenhas, C.M.; Miller, S.P.; White, P.S.; Angew. Chcm. 1n.t. Ed., 2001, 40, 601.
M]e+:
+Me
CQMe
,02
(>15
1) 70%
, O . l % Co(0Ach
5% N-hydroxyphthalimide 25"C, 15 h
* Me -zzMe
9
84% IIirano, K.; Iwahama, T.; Sakaguchi, S.; Lshii. Y, Che113. Commimn., 2000, 2457.
1. Zn , BrCH2C02Et,BFyOEt, 2. BzzO2 Chattopadhvay. A.; Salaskar, A. Synthesis, 2000, 561.
CO,Et
92%
Section 327
Alcohol - Ester
521
C I 12c12 , E t3N( GF ,3CIIzCh)2Sn 0 P h c Bucher, B.;
o
75 X80%
?‘sC1,50 min ,rt
H
TetrulzedronLttt., 2000, 41, 9617.
Fe3+-Montmorilbnite ,TsOH
76%
DCE, reflux
&OH
Choudary. B.M.; Chowdari, N.S.; Kantam, M.L. Tetlnlzcdrnn, 2000, 56, 7291.
20%
Lnb. T.-P.;
Feng, L.-C.; Wei, L.-I.. Tetrulieriron, 2000, 56, 7309. PhCHO ,TIIF, r t , 3 h
70%
*
20% PPh3
MLSV
P
h
Matsukawa, S.; Okano, N.; h a m o t o . ’I 1 Tctruherlrorr LcJtt.,2000, 41, 103. CgH &HO , 100 atm supercritical CIIF3
M%SD t-BUS
&
Tetrulzedrnn Lett., 2000, 41, 1931.
2.5% [RhCl(cod)]z , 6.5%R-BINAP laylor, S.J.;Duffey, M.O.; -.I.
,
.
>
.
9H
CIIZ=CIICOzPh , Et,MeSiII
PhCIIO
. .
. . .
t-B 46% (94:6 S:R)
. . Mlkaml.; Matsukawa, S.; Kayaki, Y.;
; -
t
0.2 [RBINOL-Ti( Oi-Pr)2C12]
I’h
A C O Z P h
E-
72% (3.4:1 sjn:unti) 8 7 7 e 34%ee Am. Cl~enr.Soc., 2000, 122, 4528.
Khau, V.V. Tetrulzedron Lett., 2000, 41, 3773.
Compendium of Organic Synthetic Methods, Vol 11
522
Section 327
pyB-Br S02Ar
.
SQAr
PbS -CQt-Bu
p --
p,,,\t~''
*
2. DIPEA , DCM Ar = 3,5di-CF3-qH3 3. PhCHO ,-78°C Corev.;Choi, S. Tetruhedron LL'tt.,2000, 41, 2769.
P
h
y SPh
COzr-Bu 97% (98:2 anti:syn) 90%ee
OMe
PhCH0
I
10%BINOL-Zr =tidyst bluene ,0°C
(8:92 syn:unti) 61% 93% ee Ishitani, H.; Yamashita, Y.; Shimizu, H.; I99: 1 unti:syn) Tetruhedron, 2001, 57, 987.
Alcohol - Halide
Section 329
53 1
1, , D C M , f l
*
cat Py-containing macrocycle Niknam, K.; Pooyan, M . Tetruhedron, 2001, 57, 6057.
I
A
80%
\2 /
T i c 4 , acetone , 1 h * 0
DCM ,1WC
N
W
71%
Shi. M,; Jiang, J.-K.; Chui, S.-C. Tetrulzerlron, 2001, 57, 7343.
or1 -
BH3*SM%, t o l u e ~ 110°C ,
-* &el 30% chird phosphoiuinide Ph
0
90 inin
0: 94% (82%e e , S)
Bdsavdlah.; .. , Reddy, G.J.; Chandrashekar, V. Tetruhedron Asyntm,, 200Z, 12, 685. 1. SiCI4, DCM ,-78°C , 4 h 10% chiral diazaphosphonmnide
Keymontl, S.; Ixgrand, 0.;Brunel, J.M.;
0
*
2. K F ,KII,PO,
% ,,,
77% (>99%ee) Eur. J. Org. Chctm., 2001, 2819.
0 F3CACOzEt
N
H H
. 10% chiral Cucoinplex ,,
ether, 0°C .-, it
C0,Et
80% (83%ee) Zhuang, W.; Gathergood, N.; Hawll, K.G.; Jorgensen, K.A. J. Org. Chem., 2001, 66, 1009.
L
Ph
1. TiCh-B u4NBr , DCM
2. i-PICI-IO
+
P
h
3. 1130+
Br 60% (>99:1 syn:nnti) Han, Z.; Uehira, S.; Shinokuho, H.; C),shima.K..Or&. Clzem., 2001, 66, 7854.
w
532
Section 329
Compendium of Organic Synthetic Methods, Vol 11
itcoP
NaBr , H 2 0 , InBr, ,40°C
pH 2 . 0 , 1.3 h
C3H,
*
&02H
s
78%
C3H,
OH Amantini, D.; Fringuelli, F.; Pizzo. F,; Vaccaro, L. J. Org. Chem., 2001, 66, 4463.
no catalyst (99 : 1) 99% + I n a 3 , pH. 15 (2 : 98) >99% 30 min Frineuelli. F.; Pizzo, F.; Vaccaro, L. J. Org. Client., 2001, 66, 4719.
ji
0.5% [Rh(S)Cy , Cy-oxo-ProNOP)
ozcCF3h
ca13
F3 C
20 atrn 112 , toluene 3O0C, 20 h
-1 F3
c
98% (97% e e , R )
Sakarnaki, Y.; Iseki, K. Org. Lttt., 2001, 3, 457.
;
PhCHO
CF31, hv , 12 h DMF ,-20°C + rt
cd 113
*
78%
MNMe2
MezN
PhCF'3 Me2N NMe2 Usher, L.C.; Estrella-Jimenez, M. Org. Zxtt., 2001, 3, 4275.
n;
A
Ph
1. CF3SiMe3,0.05 Bua+Ph3SnF2DCM , 0°C
SiMe,
2. PhCHO , BF,*OEtZ
* PhV
78% kfehvre, 0.;b i g a u d . T.: Portella. C. J. Org. Chertt., 2001, 66, 1941.
P F
h F
Smietana, M.; Gouvemeur, V.; Mioskowski, C. Tetmltedran Lett., 2000, 41, 193.
Section 329
Alcohol - IIalide
533
Ql:
1.2 10% eq TMSCl (SIIO),~ , CII,Cl, , 2 eq B'l'SP , 2 d
,,&
92%
2. IIC1MeOI-I BTSP = Me,SiOOSiMe, Sakurada, I.; Yamasaki, S.; Giittlich, R.; Iida, T.; Kanai, M.; Shihasaki. M. J. Am. Chin. SOC., 2000, 122, 1245.
uo"
Ph$H+ Br- , E M
76%
-90°C. 43 inin
% ,',,
Afonso, C.A.M.; Vieira, N.M.L.; Motherwell, W.B. Synlett, 2000, 382.
Br
1 . CH212, t o l u e ~ ~-70°C e,
*
2.
MeLi, ether NIIdC1, -70°C Bessieres, B.; Morin. C. Synlett, 2000, 1691.
4
Tt
&I
55%
1. TMSCl , DCM , 0"C, 2d 10% chiral phosphonamide
2. KF , KIIZPOI
J.M.; Buono, G. Tetruhetlron Asymn., 2000, 11, 4441. cslI1 ~
x
LiBr, I\mherly.\2-15, ~ 2h ~acetone -
~
;
~
-gr
W I I
97% Antonioletti, K.; Bovicelli, P.; Fazzolari, E.; Kiehi. G. Tctruhedron Lett., 2000, 41, 9315.
P *
.
17) 78%
(83
. .
Shlmlzu.,Kanemoto, S.; Nakahara, Y. Hercrocyclcs, h
w
o
Iz , Mn (salen) catalyst DCM, r t , 6 h
2000, 52, 117.
*
P
Naeimi, H. Bull. Chcrit. SOC. Jpn., Z9YY, 72, 1525.
h
O
L
I 71%
534
Section 330
Compendium of Organic Synthetic Methods, Vol 11
L
2. TiCh-Bu4NI, 1. PhCI-IO D C M , -78°C
3.H30'
Ph
i
P
h
v
P
h
89% (>99: 1 syn:unti) 01-6' Lett., . 1999, 1, 1383.
Uehira, S.; Han, Z.; Shinokuho, H.;
SECTION 330: ALCOHOL, THIOL - KETONE
Jw
2 eq CPzTiCI ,'I'I1FMeOI-I
OSiMe3
b-(
PI1
Ph
86%
J. Org. Chetn., 2VVZ, Mi, 1046.
Hardouin, C.; Chevallier, F.; Rousseau, B.;
P hCHO
LoH -2
*
0
Ph
,chirid ci'own ether, 0°C
cat Ce(OTf), , H,O-EtOH , 18 h
Ph
Ph
:J 85%(82%de)
Kohavashi. S.; Hmada, T.; Nagayama, S.; Manabe, K. Org. Lett., 2001, 3, 165.
Y
cyclopentanone 20% Lproline ,,CIIC13 72 h
OHC
'o.,,
1
1 J k
0
% ,,,
" J ',t,
1) 77% 20%ee
(2.5
95% ee List. B,; Pojarliev, P.; Castello, C. Org. Lett., 2001, 3, 573.
u
[( PPh3)CuH]6 , toluene
-4O"C, 1 h
@
+
Cbiu.;Zeto, C.-P.; Eng, Z.; Cheng, K.-F. Org. Lett., 2001, 3, 1901.
80%
Section 330
2. 1. B(OI-I)3 O . l M S, HzO m I ~ F0°C ,
SEN f-
TMS
(-+
Bode, J.W.; Carreira. E .M.Org. L.ett., 2001, 3, 15x7.
'rest B
oyT 535
Alcohol - Ketone
b
TMS
-%
acetone, MS 4,&, 5°C his-amnine ligarid , TIIF
.m;Silcoff, E.R.; Ito, 11. Org. L e t t . ,
2001, 3 , 2407.
62% (87% ee)
NaBII,, EtOIl , 10O"C,4 h aq dianine , PhB(OH),
P
h
v Ph
*
Ohtsuka, Y.; Koyashu, K.; Ikeno, T.;
>
CHO
Ph
5% ketoiminato cohalt complex
93% 95% anti 199% ee Org. Lett., 2001, 3, 2543.
0
1WuZn complex 36 h , -40°C
Ph
OH
I' (5 :1) 92% Yoshikawa, N.; Kumagai, N.; Matsunaga, S.; Moll, G.; Ohshima, T.; Suzuki, T.; Shihasaki.. . I Atn. . Chem. SOC., 2001, 123, 246G.
YIPll MS 4 w ,TI-IF, 15% R3PS 5% dinuclear Zn catalyst -35°C. 1 1 d
-
94% (90% ee) .Trost.;Ito, H.;Silcoff, E.R. J. Am. Chcin. SOC., 2001, 123, 3367.
Ph
536
Compendium of Organic Synthetic Methods, Vol 11
r
?Me
; Lam, Y.-F. Org. Lett., 2001, 3, 3535.
Ghorai, B.K.;
Section 330
OH
64%, 0.25% Rhz(cap)4 , PhH , reflux, 10 min 5% Rh2(OEt)4, YhH , retlux , 10 rnin 62% Hwu. J.R.; Tsay, S.-C.; Lin, L.C.; Chueh, L.L. J. A w . Cl?cin. Soc.,2001, 123, 5104.
(6.7 1) 77% (1 73) 66% . ; Sugae, T.; Ohtaka, A.; Takai, Y.; Tanaka, A,; Machino, C.; Kamhe. J . Am. Chem. SOC.,2001, 123, 5108. u/
1.5eq NaOMe
u/ 2.5 eq NaOMe
Sugoh, K.;
K;
LCIIO 5 % Co(dpm)2 PhSiH, , DCE , rt
Ph
*
)I&
Ph
70%
mph
Baik, T.-G.; Luis, A.L.; Wang, L.-C.; msche. M..1. J. Am. Chiwt. SOC.,200Z, 123, 5112. 1. PhCAO ,cat HNTf2 ether, -78°C
* 2. 1M HCl ,THF Ph Ph Ishihara, K.; Hiraiwa, Y.; m o t ( > . Ii, Synlett, 2001, 1x51
92%
Section 330
Alcohol - Ketone
A
4
PhCIIO, CHZCl2 5% VO(OSiPh),
-
Ph
537
*
,Me
Ph
Ph
Me
86% (8020 syn:unti) Trost. B.W; Jonasson, C.; Wuchrer, M. J. Ant. Client. Soc., 2001, 123, 12736. OSi(OMe),
chiral phosphine PhCHO , 10%~ AgF , BINAP derivative
MtOII 87% (7030 Jyn:ruzti), 90% ee Yanagisawa, A.; Nakatsuka, Y.; Asaknwa, K.; Kageyama, H.; Yainarn oto. €LSynlett, 2001, 69.
orr
5% Ru(PPh3)3IICl, THF
72% (56:44 syn:unti) Uma, R.; Davies, M.; Crkvisy, C.; GrBe, R. Tetruhedmn Lett., 2001, 42, 3069.
A
UBU
t-BuC€IO, 3% chiral Ca complex EtCN-?’FIT; , 20 h
Ph
=
Ph
74% (81% e e , R ) Suzuki, T.; Yainagiwa, N.; Matsuo, Y.; Sakamoto, S.; Yiunaguchi, K.; Shihasaki, M . ; U Tetruherlrnn Lett., 2001, 42, 4669.
+
2.2 tq SinIZ,THF ,rt , 4 h EtOzC+ CO2Et Liu, Y.;
Ph
Tetruhedmn LL’tt., 2001, 42, 5745.
COzEt
€* 1p 0 68%
Ph
Section 330
Compendium of Organic Synthetic Methods, Vol 11
538
1.;2;zIii;HF
/
@+ @
2. H,O+
4%
CN
H
H
77%
. . Kakluchl.; Fujioka, Y.; Yaniamura, H.; Tsutsumi, K.; Morimoto, T.; Kurosawa, H. Tetruhedron Lett., 2001, 42, 7595.
LaliC, G.; Petrovski, 2.; GaloniC, D.; MatoviC, R.; SaiEiC. R .N. Tetruhedron, 2001, 57, 583.
\
\
C0,Me
26) 78%
(74 66:34syn:unti Loh.;Feng, L.-C.; Wei, L.-L. Tetruhedron, 2001, 57, 4231.
UPh
PhCI-I0 ,Ti& , EtCN
PhL
I
-95°C
. . Shlmlzu.; Kohayashi,
-1O"C, 5.5 h
*
F.; Hayakawa, R. Tetraheriron, 2001, 57, 9591.
hv ,DMPBI , AcOH ,THF
Ph%,#\%\Ph
Ph
DMPBI = 1,3-dimethylhenziiilidazoliiie *
76%
AxPh
Ph
.. EL;Chiba, N.; Nakajima, A.; Suzuki, K.; Yoneoka, A.; Iwaya, K. flL,epawa. Synthesis, 2001, 1248.
96%
539
Section 330
PhCHO, 10% Zr(0t-Bu), , THF -2O"C, 2 d 80%
Hansch, M. Chern. Comrriiin., 2001, 1218.
OTMS
I' hCI I 0
50% '
Komoto, I.;
UPh
, PEG(OMefi, COz
%(or&
*ph
,5 o " c , 3 h
72%
Chern. Con11111m., 2001, 1842.
PhCE-10, Ti(Oi-Pr)*chiral Schiffhase
n -
DCE
C02i-Pr
Ph
e
62% (56% ee) Ilavashi. M.; Yoshimoto, K.; IIirata, N.; Tanaka, K.; Oguni, N.; Harada, K.; Matsushita, A.; Kawachi, Y.; Sasaki, H. Isr. J. Chenz., 2001, 41, 241.
0
OSi( OMe),
PhCIIO , cat R-BINM-AgF MeOH, -78"C, 1 h
Ph
64% (7 1: 29 syn:unti) 71%ee 40%ee Yanagisawa, A,; Nakatsuka, Y.; Asakawa, K.; Wadamoto, M.; Kageyarna, H.; W o t o . Bull. Chem. Snc. Jpn., 200Z, 74, 1477.
*$
%#,
1. T i c 4 , i-PrzNEt, E M , -10°C 2. i-PICHO , DCM ,-78°C
Me
MeO'
Calter.;Guo, X.; Liao, W. Org. Lett., 2001, 3, 1490.
%* % '/
% ' #,
N \Me
70% (74:26 syn,syn:syn,anti)
0a
Compendium of Organic Synthetic Methods, Vol 11
540
Section 330
ffI0
, x M
* 0
2
N
T
P B u ~, -78°C. 12 h
80% C1 NO2 UM.; Jiang, J.-K.; Cui, S.-C.; Feng, Y . 3 . J. Chent. Soc., Perkin Truns. 1, 2001, 390. 10% Cu-bis-oxzolidine ligand
c
~
~
ether, E ~ 10% Me2NPh ,rt
Juhl, K.; Gathergood, N.; ,!@ensen.
0
I
K.A. Ckcm. Conmun., 2000, 221 1.
PhCl ,reflux Id
*
t-B u 0 O t - B ~ 80%
Motherwell.;Vhzquez, S. Tetruhcrlron k t t . , 2000, 41, 9667.
*
WP.; Payne, A.H.; Waring, M.J.; Scott, D.A.; Lynch, V . Tetruhedron k'tt., 2000, 41, 9125.
O
H
\ O /N
C
0
acetone, 30% S-prohe* 2 ' DMSO
k s t . B.; Lerner, R.A.; Barbas In, C.F. J.
0 2
0
hi.
68% (76% ee) Cherri. SOC.,2000, 122, 2395.
Alcohol - Ketone
Section 330
1.
0
54 1
, 3 q T E l , , CEI,Cl, ,-50°C
2. € 1 2 0
- &LOH 46%
LaliC, G . ; Petrovski, Z.; GaloniC, D.; MatoviC, K.;SaiEiC, R.N. Tetruhedron Lett., 2000, 41, 763.
PhCHO
MeCHO , BFD ,ThDP Ph
pH 7 buffer
-
01I
BFD = henwylfonnate decailioxylase ThDP = thianun diphosphate
99% (92% ee) Eur. J. Org. Chern., 2000, 2161.
Dunnwald, T.; Demir, A S . ; Siegert, P.; Pohl, M.;
Ts
TS
win. S.W.; Chen, P.; Nikolic, N.; Weinseimer, D.C. Org. Lett., 2000, 2, 1193.
Ni(R) , TIIF, rt ,401nin
LCH0 +
Ph
Ph
Barrero.A.F.;Alvarez-Manzaneda,
L
O
H
89% E.J.; Chuhboun, R.; Meneses, R. Synlrtt, 2000, 197.
1 . PhCHO 'I'iOt-Bu2 , BINOL-
eIII$
2. R-mandelic acid II 0 Ph M d h r w a l d . O r g . Lett., 2000, 2 , 401 1 .
(9 1
5 ) 71%
Ph
Section 330
Compendium of Organic Synthetic Methods, Vol 11
542
1. 3% [CuH(PPh3)]6, PMHS , rt toluene , 3 0 h
&
CSHI 1
2. CsHIICHO ,Tic14
-Ic
72%
Chirsman, W.; Noson, K.; Papa, P.; Sclafani, J.A.; Vivian, R.W.; Keith, Tetruhedron,2000, 56, 2779.
-B.H.;
h
J.M.
S d z , PhCHO , THF ,-45°C
-
Ph
p
h
y
7
0
%
Mukaiyama, T.; Arai, H.; Shiina, I. Chezerri Lelt., 2000, 580.
'k
A( +phJy
chiral Ru catalyst , l O T , 1 di Ph
Ph
HCOOH ,NEt,
0
ori
0 11) 99% 12%ee
(89 99% a? Koike, T.; Murata, K.; W v a . T, Org. Lztt., 2000, 2, 3831.
4
Ph
0 1 . 2 q S d 2 , THF ,rt
82%
Ph
Zhou, L.;
Synth. Corrmun., 2000, 30, 597.
cat ZnBr2 ,DCM ,rt 8h
Tu.
c
t
91% OH Y Q ; Fan, C.A.; Ren, S.K.; Chan, A.S.C. .IChenz. . Soc., Pet-kin Truns. I, 2000, 3791.
Section 330
M
SiQ,
543
Alcohol - Ketone
1. PhCHO , 10% chiral phosphoranide DCM ,-78°C 2.
NaHCO,
Denmark.;Stavenger, R.A. J. h
Ph
i .
Cltern. Soc., 2000, 122, 8837.
92% ( 1 2 3 1 SIR)
oms
PhCIlO
dp,l
, 20% Pb(OTf)2, 1 d
24% a o w n ether, aq EtOII , 0°C
Nagayama, S.; Kohavas . hi. S. J. ,4111.
PhCIIO
7
* P
h
v
P
h
62% (90:lO vvn:cmti) 55% ee Chcrit. Soc., 2000, 122, 11531.
, Tic4 , NEt, , 2 d
HOu DCM ,-20°C
80%
Shi. M.; Jiang, J.-K.; Feng, Y . 4 . Org. Lxtt., 2000, 2, 2397. PhCIIO , chkal A1 catalyst
4
62%
DCM , r t , 43 h
Ph Simpura, I.; Nevalainen. V, Angew. Clieiii. In?. Ed., 2000, 39, 3422.
C3H$3I 0
Trost.
2
acetophenone , 5% c h i d ligand 10% EtZZn, 15% Ph3P=S
*
TIIF,MS 4A
Ph
C3H7
33% (56% ee)
B.M;Ito, H. J. Am. Cherrr. Soc., 2000, 122, 12003. PhCIIO , 2 eq BqSnII 0.1 CuCl ,ether , rt
*
V
P
Ooi, T.; Doda, K.; Sakai, D.; Maruoka. K. Tctruhr4ron Lett., Z999, 40, 2133.
h
72%
544
3 EmcloBn 'Livows phv 0
Compendium of Organic Synthetic Methods, Vol 11
Section 330
1. LDA ,THF , -78°C
OBn
*
2. EtCHO
B nO
B nO
B nO
(5 8 f(lm.; Hong, S.D. Tetmherfron Lett., 2000, 41, 5909.
42) 80%
PhCIlO , 10% SC(O3SC12€{25)3
Ph
10% IICl, H 2 0 , 2 7 " C , 3 11 *
82%
35% yield without IlCl Manahe, K.; Xohavashi. S, Tetruhedron Lftt., 19Y9, 40, 3773.
kI?.CHO, TiCl.+Bu3 0.05 TMSCl ,CH2C12
87%
Yoshida, Y.; Mahumoto, N.; Hamasaki, R.; Xitube. Y, Tetruherlron Lett., 1999, 40, 4227.
P h x c H o
Ph
, 8% chii-41Li cahlyd
* Ph
M M D S , 16%;1120, 1HF , 18 h Yoshikawa, N.; Yamada, Y.M.A.; Das, J.; Sasai, II.; J . Ant. Chem. SOC.,1999, 121, 4168.
L
t- BU
83% (85% ee)
1. R-BINOL-SEM, SnCh CIJzClz, -125°C 4 -78°C: 2. HI;-pyiidine , THF
* ~-BU%~~
Ishihara, K.; Nakamura, H.; Yamamoto. H , J. A m Chern. SOC.,Z999, 121, 7720.
87~95%
Section 330
Alcohol - Ketone
545
phvo
potassium monoperoxysulfate KzC03, pII 10.5 , MeCN , 0°C
I
Addm.;Saha-Moller, C.R.; Zhno, C.-G. J.
I
Org. Cliciiz., 1999, 64, 7492.
1. t-BuLi, T I I F , -78°C
mDMsL t
2. cyclohexanone ,I’I-IF -78°C
B
HZO, TIIF
-
lI+kI.-c”
M
%
S
i
72%
€30
Ph
Howell. A .R.;Ndakala, A.J. Org. Lttt., ZYYY, 1, 825.
GI%
+
e
co,I I
20% hC13 , 2 d ultrasound
(84 5 6 :44 syn:unt i Loh. T.-P.;Wei, I,.-L.; Feng, L.-C. Synlett, ZYYY, 1059.
I-IO,C 16) 95%
woSiMn, Pll
PhCIIO
u
. J. Org. Cliem., 1999, 64, 7547.
Stergiades, I.A.;
)$
-
a1 EtOH , -10°C
74% (3.2 : 1 syn:anti) 67%ee I-Pr i -Pr Kohavashi. S.; Nagayama, S.; Busujima, T. Cl~eiit.Lett., 1999, 71. +,% .
w
Compendium of Organic Synthetic Methods, Vol 11
546
PhCHO
Section 330
benzoyl fonnate decarboxyhse
* Ph
aq lwffer
70% (>99% ee)
Tetruhedron Asymm., 1999, 10,47G9.
PhCHO 20% chin1 his oxamline , 20 h 74% (3.2 : 1 syn:anti) 67% ee KobJuashi.: . . Nagayama, S.; Busujima, T. Tefruhcdron, Z999, 55, 8739.
PhC€IO
m.
+OTMS PI1
,H20
*
uph 87%
activated Monhnorillonite Ph K-10 clay T.-P.; Li, X.-R.Tetruhedron, 199Y. 55, 10780.
A 88% (GG% ee)
IIanzawa.;Tahuchi, N.; Saito, K.; Noguchi, S.;
Angew. Chem. Int. Ed., 1999, 38, 2395.
0
OlMS
PhCHO
,5MLiC104
MeN02,4 h
Sudha, R.;
*
(yPh
PhCHO , Et2A10Et,TIIF, 0°C z
85%
nPh
J. Ch~wi.Soc., Porkin Truns. 1, 1999, 383.
0 OH Mukaiyama, T.; Shihata, J.; Shimamura, T.; Shiina, I. Chern. Corrtmrtn., 1999, 951.
74%
Section 331
Alcohol
- Nitrile
547
PhCHO ,(B~3Sn)z
P& h,h€'
Bu,SnCl,, xi THF 0
Shihata, I.; Kawasaki, M.; Yasuda, M.; P,(\/~~''
81% (75:25 syn:anti) Chern. Lett., 1999, 689.
, E M ,-23°C
6 tw Ph+Br
OH
0
'I'iClz-Cu , t-BuCN , 3 h
94% (91:9 syn:anri) Mukaiyama, T.; Kagayama, A.; Igarashi, K.; Shiina, I. Chenz. Lxtt., 1999, 1157.
AlCI3 , PhCl , 106°C
/
mimwavcs , 3 min
/
+
o
73%
e
O
\ /
H
23%
Khadllkar.; Madyar, V.R. Synth. Coninrun., 1999, 2Y, 1195 REVIEWS: "Diastereoselection in Lewis Acid Mediated Aldol Additions," Chem. Rev., 1999, 95, 1095 "The Vinylogous Aldol Reaction: A Valuahle, Yet Understated Carhon-Carhon Bond Forming ; Zanardi, F.; M o n o . G.; Rassu, G. Maneuver," Chenz. Rev., 2000, 100, 1029.
SECTION 331: ALCOHOL, THIOI, - NITRILE
PhCIIO
3.5 eq IICN , it, pH 4 5 PVAI.entiapped R oxyni&ilane
t
f"
hiphasic, MTBE-hexane Ph*CN WH.; Capan. E.; Buthuher, A,; Vorlop. K.-D. Org. Lett., 2001, 3, 1969.
85% (95%ee)
548
Compendium of Organic Synthetic Methods, Vol 11
Section 331
3% Mn(dpm)3 , CPrOH , 1h 0 2
&,!nus.
,PhSR3
PJ Scott, D.A.; Fielding, M.R. Tetruherhn krt., 2001, 42, 4127.
*r
1. [InBr/C13CCN] /I,HO
2. H,O+
54%
*
70%
Nbhrega, J.A.; GonGalves, S.M.C.; Penne. C. Tetrulaerlron Lett., 2001, 42, 4745.
CHO
1. TMSCN , DCM , 3 6 h ,-40"C B u ~ P Ochkal , Al catalyst
01I
-
)r
Ph-
2. 2N MCl
6 CN
Ph
97% (97% ee) Hamashima, Y.; Sawada, D.; Nogami, H.; Hanai, M.; Tetruhedron, 2001, 57, 801.
1,
1. TMSCN , 20%JTi(Oi-Pr), , J X M
PhCI-IO
chird Schiff base , -40°C
2. H+ Y ~ I I2.-€1.; ~ , Wang, L.-X.; Zhou, Z.-H.; Zhou, Q.-L.; T Tetruhedron Asyr,lm., 2001, 12, 1579.
+CN
1. CeC13 , TIIF
~
98% (70% ee)
Ph
~ D PC . - C .
&CN
+
L
Ph
P 11 (15
Dalrrozzo.;Bartoli, G.; Bosco, M.; DeNino, A.; Procopio, A.;
N
--
2. LiBII, Ph
C-
85) 75% Samhri, L.; Tagarelli, A.
Eur. J. Org. Chent., 2001, 2911.
IICN ,pHS.O, 1 , C , 12h R-hydroxynikile lyau:
Gerrits, P.J.;
H
O
a
\ /
Y
72% (86% ee)
N
Marcus.; Birikaki, L.; van der Gen, A. Teti-uherlronAsymm., 2001, 12, 971.
Section 33 1
PhCHO
Alcohol
549
- Nitrile
----
1% Li-R-(+)-BINOL TMSCN , 5 rnin
QmfS
h
96% (56% ee,S)
Ph+CN Ilolmes, I.P.; Kanan. H.B. Tt.tl-uh~~drnn Lett., 2000, 41, 7453.
xcN
(0
1) 95%
Ward.;IIrapchak, M.J.; Sales, M. 01-8.Lett., 2000, 2, 57. BlCIIzCN , 2 TIIF
LXI
87%
SI~II,
Tctmherlron Lett., 2000, 41, 3039.
PhCI I 0
YOU,J.-S.;
Me,SiCN , Ti(Oi-Pr), , 2 d
--
xcN 67%
cat p-amino-alcohol sulfonato derivatives Ph DCM , MS 4 i i - ; Choi, M.C.K. C h ~ l Conmiin., . 2000, 1963.
1 . TMSCN ,YC13(R-pyliox)z
PhCHO
2. 1 MIICl
77% (80% ee) CN pyhox = hk-(oxazolidinyl)p).rid~e Asmnall. H.C... GreevesI . N.; Smith, P.M. Toti-uhedron Lett., 1999, 40, 1763.
Ph
(Yo
10% I'(KNCII2CH2)3N , MeCN 2 . 2 t ~ MgS04 l ,25"C, 4 h
*
Dm 94%
Kisanga, P.; McLeod, D.; D'Sa, B.; Verkude. J, J. Org. Clzeni., 1999, 64, 3090.
I'h
A
10% Ce(OTf)j , NaCN
M K N , 70°C. 1 d
CN 011
70%
Iranpoor. N.; Shekarriz, M. Synrh. Cmnniiin., 19Y9, 2Y, 2240.
+
CN
12%
Section 332
Compendium of Organic Synthetic Methods, Vol 11
550
-
SECTION 332: ALCOHOL, THlOL ALKENE Allylic and benzylic hydroxylation (C=C-C-1-1 Section 41 (Alcohols from Hydrides).
-f
2
LDA, THF ,-78°C
C=C-C-OII, etc.) is listed in
+
HO-CN
4 eq ALOH , 5 inin Fleminp.;Wang, Q.; Steward, O.W. J. Org. Chem., 2001, 66, 2171.
u
83%
-b Ts
TsBr , AIBN , toluene
CsH11
90"C13 h
1
u, KO, B.-S.; Ha, Y.-€3. J. Org. Client., 2001, 66, 3630.
-P-
75%
OTMS
i-PiCHO ,TIIF, it , 1 d
OEt
,
Bluet, G . ;
I
*
chiral ainimniuin lluoride
I
-
70%(20%ee) J. Org. Clieni., 2001, 66, 4293.
65% (90%ee) Oppolzer, W.; Radinov, R.N.; El-Saved. E, J. Orhp. Client., 2001, 66, 4766.
CaH13Y-Y Br
CICI, ,NiClz , DMF ,rt
0
Trost.;Pinkerton, A.B. J . Org. CIwnt., 2001, 66, 7714.
9 70%
Section 332
55 1
Alcohol - Alkene
1Y k
C3F7
20% PhCHO
TMSO
1-1B- 0
-
,EtCN, -78°C
,syiinge pump
I
1:2(E:z)
71%
u; Wei, H.-X.; Phelps, B.S.; I k k i s s , D.W.; Kim, S.H. Org. Zxtt., 2001, 3, 823. CHO
CI-I2=CIICN,TCI4 Bu4NBr, E M , 20°C
Shi. M.; Feng, Y . 3 .J. Org. CIwnr., 2001, 66,406. (i
{:
OJON(
NOC 0, I. BuLi, pentane (-)-spmteine , -78°C +
2. TiCl(Oi-Pr), , -78°C 3. i-PICIIO , -78°C
MqSi
i-Pr)
,,,,+'
MqSi
i-pr 76% (>95% ee) Schultz-Fademrecht, C.; Wihheling, B.; Friilich, R.; Boppe. n. Org. k t r . , 2001, 3, 1221. n
Koh, J.H.; Larsen, A.O.; GaenC. M.R. Org. Zx:tt., 2001, 3, 1233.
Denmark. S.E.; Yang, S.-M. Org. Lc)tt., 2001, 3, 1740.
77% conversion (77% ee)
Section 332
Compendium of Organic Synthetic Methods, Vol 11
552
p
h
s u g a r 4
@ OH
0
Kr&uJ&.;
Kannan, V.; Ilnngovan, A.; Shaima, C.V.M. Tetruhedron Asyrnnt., 200Z, 12, X29.
NO2
91% (40%de ,R )
Kang. S.-Y;Ryu, H.-C.; Hong, Y.-T.; Kim, M.-S.; Lee, S.-W.; Jung, J.41. Synth. Conimun., 2001, 31, 2365.
1. 2-( lithiomethyl)-l-methylnnidau,le + chiral I i a n i d e , TNF
96% (93% ee)
2. H,O+ Idill, S.O.N.; Fettersen, D.; Amedjkouh, M.; Ahlhere. P. J . Chent. Soc., I'erliin Truns. 1. 2001, 3054.
Takai. K; Kokumai, R.; Nohunuka, T. Cherri. Conrrrirtn., 2001, 1128.
b
84%
Section 332
Compendium of Organic Synthetic Methods, Vol 11
554
CH3CHO
1. B r u C O z M e ,In ,
THF , HC1
2.DBU ,F%H
*
?TM
64x881 (93:7 E:Z) Cha, J.W.; Pae, A.N.; Choi, K.I.I.; Cho. Y.S.; Koh, H.Y.;Lee. E. J. Chcni. SOC., Perkin Truns. I , 2001, 2079.
87% ( 1 . 9 1 ) Wendling, F.; JVliesch. M, Org. L.ett., 2001, 3 , 2689.
m
II
CHO In,DMF,rt
SiMe,
89% Lee. P.H.; Bang, K.; Lee, K.; Lee, C.-11.; Chang, S. Tetruhedrun L d t . , 2000, 41, 7521.
Mn ,1076 CfiTiClz 2,4,6-collidine*HCl THF
Gdnsduer.; . .< Pierohon, M. Synlett,
20011, 1357.
u; Wei, I-I.-X.;Gao, J.J.; Cuputo, T.D. Tctrdierlron Lett., 2000, 41, 1.
75%
555
Section 332
7, \
0
Ag:KI, AcOH reflux, 30 min
0
O
g
0
-
Sharehi.;Aghapour, G . J. Org. Cliein., 2000, 65, 2813. 10% PhCIIO , 10% Sn(Oi'),
QH
CHZCI,, 0°C , 2 h I
78% (4911, E/z) Sumida, S.-i.; Ohga, M.; Mitnni, J.; J'Jokaini. J . .I. Am. Clzenz. Soc., 2000, 122, 1310.
Kim, M.S.; Kim, T.Y.; Lee, K.Y.; Chung, Y.M.; Lee, I1.J.; Kim. J.N. Tetruhedron Lxtt., 2000, 41, 2613.
LautLns.;Renaud, J.-L.; Hichert, S. J. a
.
92% (>98% de) Am. Clreni. Soc., 2000, 122, 1804.
PhCHO , S% PdCz(PPh3)2 IICI-SIICI~ , DMF ,rt Chatlg, II.-M.;
1
C.-FLClrg. Lett., 200fJ, 2, 3430.
>99%
556
Compendium of Organic Synthetic Methods, Vol 11
Br
P hCHO
In , 1120
Section 332
Br
'
* ph+% Lu, W.; Ma, J.; Wang, Y.; Chan, T.H. Org. LEtt., 2000, 2, 3469.
f f Y
v
2. NaOII
* ,11202
1
II
- . . Laldlewlcz.; Krczemimski, M.P. Org. Lett., 2000, 2, 3897. Et02C-CHO , 10% Pd catalyst DCFJtoluene , 6O"C, 4 h
PI1
=
97% (88% ee)
Org. Lm. 2000, , 2, 4059.
Hao, J.; Hatano, M.;
PhCIIO , 10% Ni(cod)2 Me
-
Ph+ph
20% PCy, , 2 BE t3 toluene, 23°C IIuang, W.-S.; Chan, J.; Jamison. T.F, Or$. Lett., 2000, 2, 4221.
7
,cat N i ( a ~ ; l c ) ~
P hCI 10
M q B , TI-IF, 2 11 Kimura, M.; Shihnta, K.; Koudahashi, Y.; Tainaru.
A
Ph
-
-78"C, 2 h
76% (77:23)
TP 56% (20:l E:Z)
Y.Tm-uherli-onL m ,2000, 42, 6789.
CM2=CIIMgBr, CeCl, , THF SiMq
fi
* & Ph
SiMe3 Bonini, B.F.; Comes-Franchini, M.; Fochi, M.; Mazzanti, G.; Ricc.i.; Varchi, G. Synlett, 2000, 1688.
60%
Section 332
Alcohol - Alkene
K =CRI
557
c~H7(B >
1. sec-BuLi, TMEDA ether, -78°C
N(i-Prh
2. Ti(Oi-Fr), ,-78°C 3. C$&IIO ,ether -78°C0°C
N(i-Prh
0
Mark6.IE; Leroy, B. Tetr-ul?crlronLxtt., 2000, 41, 7225.
1. q2-C,II6-?'i(Oi-Pr), , ether 2. EtCIIO, ether/ffII'
*KO
*KO$2
3. €1+
SiMq
K* = camphor-hued auxiliary 95% (97:3 S:R) Suzuki, D.; Urahe, 11.; $at(). I'. Angew. Cheni. b it. Ed., 2000, 39, 3290. ser-BuLi/(-)-spaiteine ,ether -9O"C, 6 h
*
1 0
,,,,,,,,85%(62%ee)
or1 ; Vrancken, E.; Mangeney, P. J. C17c~l.SOC., Perkin Truns. 1, 2000, 3354.
Youn, S.W.; Park, I1.S.; Kim. Y .I-I. Climr. Cnrrirrzrin., 2000, 2005.
&
OPMB
OPMB
2
MeZZt1, DCE , L*
S% Pd(MeCN)2C12, heat
* G
I,* = S-t-BuSDII'OF
Lduttns.; . Hiehert, 1
.
S.; Renaud, J.-L. O q . Lett., 2000, 2 , 1071.
O
or1
P
M
OPMB
87% (91% ee)
B
558
Section 332
Compendium of Organic Synthetic Methods, Vol 11
PhI
Anwar, U.;
1. DMF , 10% Pd(0Ac)z tris(2-fury1)phosphine
Ph
2. In ' M
H
e
0
~
-*
C
Ph%
O
64%
OMe
u; Raspitiini, M.; Savic, V.; Sridharan, V. Chem. Commun., 2000, 645.
oo 1.2
2 y L D A , 5 y DBU, T H F 78% (95% ee) rt,ld Sodergren, M.J.; Bertilsson, S.K.; Andel 'sson. P.G, J. Am. Chern. Soc., 2000, 122, 6610.
PhCfIO ,70% LiCIO,
Jm2Et 15% DABCO, ether O"C,20h
Kawlunura, M.;
C,H &€I0
'
'
% h'€
81%
TotrulzorlronLdt., 1999, 40, 1539.
BH
1. MLCCI, ,CrCI,(Mn) , THF ,r t 2. LDA
Falck.
CO2Et
*
'7"15
J.B;Barina, D.K.; Mioskowski. C.; Schlama, T. Tctruhcrlron Left.,
de Sousa, S.E.;
1999, 40, 2091.
; Steffens, 1I.C. Tetruherlron Lett., 1999, 40, 8423.
OH
TIIF, MS 4A,~t 2.PhMe, 5 % B H T , 190°C 3. M q N O , PhH ,XO"C
Batev.;Thadani, A N . ; Lough,
1111111111
HO
HO 75) 80%
A.J. J . Am. Chem. Soc., 1999, 121, 450.
559
Section 332
-
yuan, L.G.; -an.
100°C C~H&KCIC~H ~, .5% Pd(OAc), , 2 t-BuOAc
*
DMF . 2 0 h
V . . Y, ' m. ( >to. y.J. Ani. Cheni. Soc., 1999, 121, 3545
CIJO
, 19 h
-/-SnB"3
Ph
L-
BF3.0Et2, toluene
Ph+
Luo, M.; Iwahuchi, Y.; Hatakevaina. S. Chcni. Corriinun., 1999, 267.
PhCHO
92%
LSnBy , PhCF3 S-BINOL-Ti(1V), i-PrSBEt2, -20°C
Ph+
y u . C.-M,; Lee, S.-J.; Jeon, M. J. Clwrii. Soc., Perkin Truns. I , 1999, 3557.
81% (98% ee)
1% Ru(md)(cot) , PEt3 hexane , 20"C, 4.5 h
94% (97% Z) Sate, T.; Komine, N.; IIirano, M.; &va.
S. Cltenz. Lett., 1999, 441. 0 1I
__
1 . Me,CuLi/MeMgBr-CuBr-DMS
C0,Me
2. PIICIIO
Wei, K-X.; Willis, S.; Also via:
69% (95/1 UE) Synth. Coniiiiui~.,1999, 2Y, 29.59. Section 302 (Alkyne - Alcohol).
560
Compendium of Organic Synthetic Methods, Vol 11
Section 335
SECTION 333: ALDEHYDE - ALDEHYDE NO ADDITIONAL EXAMPLES
SECTION 334: ALDEHYDE - AMIDE
PHO OMe Banfield, S.C.; England, D.B
CHO
0
N-Ac NAc
69%
Fuchs, J.K.; Funk. K.1, Org. Lett., 2001, 3, 3361
OYPh Boto, A.; IIernindez, R.;
. T ~ ~ u k e d r Lztt., c ~ n 1999, 40, 5945.
SECTION 335: ALDEHYDE - AMINE
Section 338
Aldehyde - Halide
56 1
Me
Ph
+
12) 70% 4-1 a Jen, W.S.; Wiener, J.J.M.; MacMillan. D.W.C. J. Anr. Cl~cni.Soc., 2000, 122, 9874.
SECTION 336: ALDEIIYDE - ESTER
CDzMe
-
CO/IIZ , superaitical COZ cat P @ - c ~ I I , - c ~ F , , ~ *
0 1IC
cat Rh(acac)(C0)2 , 80"C, 11 h 98% (48% conversion)
IIu, Y.; (:hen, W.; Osuna, A.M.B.;Stuart, A.M.; Hope, E.G.; Chem. Conitnun., 2001, 725.
SECTION 337: ALDEHYDE - ETHER, EPOXIDE, THIOETHER
c~IO
Ph
1 . PhS(O)CI-I(Cl)Li 2. 5 PhSII , 7 t-BuOK 98x73%
C-BuOII,TIIF, it , 10iiiin * phdSPh Satoh. T.; Kuhota, K.-i. Tc.triilieilron Lcjtt., 2000, 41, 2121.
SECTION 338: ALDEHYDE - HALIDE, SULFONATE 1. IPy2BF4, DCM , hv , rt , 12 h
91%
~
H 2. II,O+ €1 Gonzilez-Bohes, I:.; Annthouju, S.R.; Garcia-Martin, M.A.; GonzBlez, J.M. Angew. Chent. Int. Ed., 2001, 40,33x9. D
O
; . J-
c1
176 2.6-lutidine-IIC1, 3.5% HCl C3II7-CHO Bellesia, F.; De Buyck, L.; Tetruh~4ron,2000, 56,7507.
t
DCM , 65°C C,H, X I 1 ; I,ihcrtini, E.; Pagnoni, U.M.; Roncaglia, F.
59%
0
562
Compendiuni of Organic Synthetic Methods, Vol 11
Section 341
-
SECTION 339: ALDEHYDE KETONE
C,H &H2CH0, MeCN ,reflux 10% Et2NSiMq
"".+
66% CHO Uapiwara. I.l; Komatsuhara, N.; Ono, €1.;Okahe, T.; Hoshi, T.; Suzuki, T.; Ando, M.; Kato, M. J. Chem. SOC., Perkin Truns. 1, 2001, 316.
/L
1. P B u ~, TI-IF , -40°C
2. SnlT2 c1 3. 1M N C I * PhW C H O 80% Mdedd.; . . Huang, Y.; Hino, N.; Yamauchi, Y.; Ohmori, H. Chem. Commun., 2000, 2307. Ph
II
1. LDA , ether , -78°C 2. HCO,CH,CF, , -78°C
Org. Lett., 1999, I, 989
SECTION 340: ALDEHYDE - NITRILE NO ADDITIONAL EXAMPLES
REV IE WS : "Cyanohydrins in Nature and the 1,ahoratory: Biology, Preparations and Synthetic Applications," Grecorv.R.J.H. C h m . Rcv.. 1999. 99, 3649.
SECTION 341: ALDEHYDE - ALKENE For the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes froin Alcohols).
Aldehyde - Alkene
Section 341
563
OHC
CHz=CIICHO, 4% RU acllyst
-
DCM, 25"C, 12 h
Ho$
.
6
..yJ
70%
Org. LPtt., 2001, 3 , 1451.
Ph-OH
10% Pd(OAc)z, 20% PPh, 2.4 BEt, , TIIF, NEt, Licl
Kimura, M.; Horino, Y . ;Mukai, R.; Tanaka, S.; 'Jamam. J. Am. Cham. Soc., 2001, 123, 10401.
GH13
HO] CHO
=
-
Y.
Me,PhSiH, 40 atm C O , 4 0 T , 1 d
O H ~ i M e $ h 7 8 %
z
[R h+(cod)(r16-C&I $-Ph3)] C6H13 Okazaki, H.; Kawanami, Y.;Yoin:unoto. K. Cheni. Lett., 2001, 650. 1
N-NHTs
%J
2.5 eq PhMgBr
* Ph
CHO
75%
Chandrasekhar. S .; Reddy, M.V.; Reddy, K.S.; Kamarao, C. Tetruhedron ,!.eft., 2000, 41, 2667.
I
63 % Parsons,E,. I ; Thomson, P.; Taylor, A,; Sparks, T. Org. k t t . , 2000, 2, 571.
Compendiuni of Organic Synthetic Methods, Vol 11
564
Section 341
%CHO
Higashino, T.; Sakaguchi, S . ; -Orb'.
h t t . . 2000, 2, 4193.
C H Z S I I O A c , Ba(OH)2 I
P hCHO
CHO
Ph
TIIF, heat , 10 h Mahata, P.K.; Barun, 0.;IliL H.: J-p. . . Lt Synlett, 2000, 1345.
-
7 -
Kh(CO)z(acac) , PhMezSiH
78%
SiMqPh
Ph€I, CO ,90"C, 14 h ; Itoh, K. Tctruherlron Lett., IYYY, 40, 4703.
Fukuta, Y.;
65%
+
(cod)KhI-'hBPh, ,60"C P(OPhh ,CHZClz , 2 d 6 atin C O , 6 ntm Hz van den Hoven, B.G.;
A
Ph Bharathi, P.;
J. Org. Client., 1999, 64, 3961. 1 . Tic4 , DCM, NEt,
* CHO
2.1120 Org. Lett., 1999, I , 857.
0.2 pyirolidine , 0.1 PhCO2N
Bu-CHO
toluene, ZO"C, 14 h
xr
78%
Ph
-
IShikdWd.; . , . Uedo, E.; Okada, S.; &it(>. S , Syrtlett, I Y Y Y , 450.
Bu
79%
REVIEWS: "The Silyloxy-Cope Rean'angement of Syn-Aldol Products: Evolution of a Powerful Synthetic Strategy," w i d er. C, Synktt, 2001, 1070. Also via f%-€Iydroxyaldchydes: Section 324 (Alcohols - Aldehyde).
Section 343
565
An~ide- Ainine
SECTION 342: AMIDE - AMIDE
#L mCoZMe NIIAc
1. ~-NsNCI~/MLCN 2. XJ NilZS03
LL&;
C02Me
Ph
Ph
~ H N s - ~ "%
t
Kim, S.H.; Wei, I-I.-X. Tctruhedi-on Lc.tt., 20UU, 41,8609.
0
8 y S m 1 2 , TIIF 16 C X ~R-BINOL 32 eq 'IMEDA , 411 -78°C , 30 min
/
Me
Me
70% (71% ee) 2w0 Kikukawa, T.; IIanamoto, T.; Inanaca. J. Tc,truhcclr-on Lett., ZYY9, 40, 7497. Section 312 (Cxboxylic Acid - Carboxylic Acid) Also via Dicarhoxylic Acids: Section 350 (Amines - hnines) Dialnines
SECTION 343: AMIDE - AMINE
p
-
--
t-BuCIIO, NaCN, A d 1 1
H2N-lfNH2
1 1 2 0 , 70"C, I d
0
'-"";7(, m
z
y
N
H
2
0
93% (>99: 1)
n Dielemans, ; H.J.A.; Elsenberg, 1I.L.M.;
Boesten, W.1I.J.; Seerden, .l.-P.G.; Kaptein, B.; Moudy, H.h4.; Kellogg, R.M.;
A NI/"A
Org. Lett., 2001, 3, 1121.
PhNIIMe , DCM, rt 10% Ni(C10,),6 II,O his-oxazoline ligand
Zhuang, W.; IIazell, R.G.; m n s e n .&(I
ph\
/Me
JJ
76% (88% ee) Chcm. Conwiin., 2001, 1240.
566
Compendium of Organic Synthetic Methods, Vol 11
a A,,
Et,
1. Et,AICI, MeCN *
w
u
Ac C02Et
62% (75:25 anti:syn)
. M.; Niwa, Y. Tetrahedron In.tt., 2001, 42, 2829.
N -Ts
yP
E * , C Y
2. AcQ
E0,C
Section 343
PhNIIMe , acetone, rt
86%
p-cyclodextiin, 1 1 0 , 1 d
Reddy, M.A.; Reddy, L.R.; Bhanumathi, N.; Rao. K .RCherir. I d t . , 2001, 246.
AJNG
C5Hl 1
Ishihiua, H.;
N H /J ether, -78°C
CllPirt.
C5Hll
Lett., 2001, 980.
86% truns
9 0.s 9 N D YN 2eq
,Id
BuLi ,‘HIF , -78°C
0 Hori, K.; Sugihara, H.; J@. Y.N.:-
I
rt
0
Tetruhedron LEtt., I999,40, 5201.
PhI, PdlC ,NEt, , MS 4A 800 psi CO , 100 gpi Mz 120°C
87% Ph 0
Lin, Y.-S.;
82%
Angew. Chcri~Int. Ed., 2001, 40, 719.
Section 343
567
PLlnide - Amine
n
-
23% 44% Hadden, M.; Nieuwenhuywn, M.; Potts, D.; Stevenson. P.J.; Thompson, N. Tetruhedron, 2001, 57, 5615.
....
1111,111
m B ( O W 2 Ph
P
B nN€ICH2CH2NHBn MLCN , 80°C. 2 h
3:) 76%
Ph
Petasis. N.A.; Patel, Z.D. Toti-uhcrlron Lxtt., 2000, 41, 9607. 0
0
Q Ph
‘o\%N
Me0
PhNH, , TIIF
45% OMe Alcaide.;Almendros, P.; Ar-ngoncillo, C. Cliern. Conirnun., 2000,757.
Bu
=
I
Bn
NHBn
Fb
OLi
Shindo.;Oya, S.; Murakami, K.;
Snto, Y.; Shishido, K. Tetmhedron Lett., 2000,41, 5943.
568
Compendium of Organic Synthetic Methods, Vol 11
Section 344
-*& HZN
I . Pd(OAc),, D P E A , DMF , PhI
2.10% TFA, CII2Cl,
ph d
8
4
%
Wanp.; Huang, T.-N. Tetruherlron LJtt.,ZY99, 40, 5837.
*a
10% TiCl,(thf), , i-Pr2NEt CHzC12, 25°C
NHPhth
NIIPlth
r__ l
77% (>99: 1 syn:ant4 Yoon, T.P.; Dong, Vy.M.; MacMill an. D.W.C. J . Am. Cliern. SOC., 1999, 121, 9726.
“I-c:l‘
1.lT 80”C, M S SI’hII, , AIBN 5h
2. H Z 0
TrMSS = tns-tiiinethylsilylsilane M Q SI
S02Me
Kizil, M.; Patro, B.; Callaghan, 0.;w
J . Org. Chem., 1999, 64,7856.
v . J.A.; IIursthouse, M.B.; Hibhs, D.
SECTION 344: AMIDE - ESTER
1 . t-BuNC, TIIF I I,CO ,H
@lo)2P(0)c Ph
CfIO
83%
t-BuHN
2. LiBr, N E t 3 , TI-IF
Beck, B.; Magnin-Lachaux, M.; I-Ierdtweck, E.;
87% ph
Org. Lrtt., 2001, 3, 2875.
Section 344
Arnide - Ester
569
NIIPMP
JPMP Ph$iO /==(OTMS OMe
Ph
C02Me
q HBF4 , sodium dodecykulfate
OSiPhl 90% (90 10 syn:unti)
4
Nuvama.,Takaya, J.; Kagoshima, H. Tetrultedron Zztt., 2001, 42, 4025.
0
,,,#’“
M t O H , NaHC03
Me02
COzMe
reflux, 10 inin NHChz h , M e ’ChZ Allevl.;Cighetti, G.; Anatasia, M. Tcrruherlron La., 2001, 42, 5319.
Ly
KN( cycbhexyl)z
Ph-N@OC),
TI IF ,-78°C
88%
C02t-Bu
- A Ph
N(Boch
92%
Kise.;Ozaki, H.; Terui, €1.; Ohya, K.; Ueda, N. Tetrul?erlron k t t . , 2002, 42, 7637. C02Me
TIIF, -78°C
I
N
.y”c
C02Me
-+
0°C
IZIICU(CN)CH~CH~CO~ LiCl M~-~
Ts
C02Me
NHTs 99% Oishi, S.; ‘Tamamura.; Yainashita, M.; Odagaki, Y.; Hlunanaka, N.; Otaka, A.; J . Chem. Soc., Perkin Truns. 1, 2001, 2445. TsNBrNa ,M t C N , rt
Ts,
NrC
cat Pd(Md:N),Cl;! * Antunes, A.M.M.; Marto, S.J.L.; Brunco. P.S.: Prahhakar. S.; Loho, A.M. Chetn. Commun., 2 0 0 1 , 405.
NI I Ac C02Me
112 , Kh (R,R)-MeDuPHS) , i-PiOH
[h~niin]PF6 ionic liquid medium
Guernik, S.;Wolfson, A.; IIrshowitz, M.; Greenspoon, N.; Seresh. S . Chmi. Conintun., 2 0 0 1 , 2314.
60%
NH Ac C02Me quant (99% ee ,R )
v
Compendium of Organic Synthetic Methods, Vol 11
570
P-ToICIIO, EtCN , 3 EtO
-78"C+
TiI4
Section 344
P-ToI
EtO
-20°C
N -Ts
NHTs
. . Shlrmzu.; Takeuchi, Y.;
74% (77:23 anti:syn)
Sahara, T. Chem. Lett., 2001, 1196. ICOzEt 5% PhNMQ, R-Tol-BINAPKuPF6 THF , -78°C
* W J + .
E02c
/
NMe, 75% (96% ee) Angew. Chem. Int. Ed., 2000, 39, 4114.
Saahy, S.; Fang, X.; Gathergood, N.;
1. LDA , TIIF t-BuO
c
rBu J +
Me
NC
A J T n s t r o ;~Atkin, M .A,; Swallow, S. Tc.truherlron .!At., 2000, 41, 2247.
20%
BnOzCHN Zn-Cu , DCM , rt Mecozzi, T.;
NHCOzB n Tetruhedron Lett., 2000, 41, 2709.
82% (28:72 antisyn)
IIZ , P d 4 , EtOAc-EtOH 30 inin
Papageorgiou, E.A.; Gaunt, M.J.; Yu, 1.-q.;
93% Org. k j t t . , 2000, 2, 1049.
Ranu.; Hajra, A.; Jana,
U. J. Org. Chcm., 2000, 65, 6270.
1 . sec-BuLi, TI-IF 2. CuCN.2 LiCl
MtiN-Boc Dieter.
571
h i d e - Ester
Section 344
Me
I
*
C02Me
3. CH2SHC02Me B~~HNLu, K.; Velu, S.E. J. Orx. Chem., 2000, 65, 8715.
u;
@'T
Ph NBS PhCl,refhx,12h , NaOAc , AcOH
*
*2: 85%
0
,Ts
NHTs
SiMq
5 % S-Tol-BINM - C U P F ~ CI r2a2
C02Me
34% (58% ee, R)
Me02
Py Q N H B o c
NaII, THF 1 .
Johnstone, S. .I.Org. Cliiwi., 1999,64,5896. OMe
EtC€I2C02Me, LDA-THF
NI4CO2Me Ti(Oi-Pr)4, -70°C
+
b
xcqN
0
2 C 0 2 M ;
N Hot-B u
76%
2 C Q M . z i-Pr
0°C i-pr NHCOlMe
Kise.;IJede, N. J. Orx. Clieiit., 1999, 64, 7511.
C02Et
H
Fang, X.; Johannsen, M.; Hao, S.; Gathergood, N.; Hazell, K.G.; J. Org. Cheni., 1999,64,4844. Me 0 2 C,,
0
Totruhedron Lett., 1999,40, 8215
Cho, S.-D.; Kim, H.-J.; Ahn, C.;
Et02C
83%
(8
NHC02Me
92) 90%
572
Section 345
Coinpendium of Organic Synthetic Methods, Vol 11
CAN, MeOH
,02
0 0 it, 15inin Nair. V,;Sheeha, V. J. Org. Ch.ern.,IY99,64,6898.
BulSnIi , PhH , AIBN
Benati.
-
k; Nanni, D.;
I;,COCH N
PhH N
-
&
70%
70%
co*Me Snngiorgi, G . ; Spngnolo, P. J. Org. Chenr., 1999, 64, 7836.
CO,t-Bu _ .
-78"C-+ rt Kazmaler.; Zumpe, F.L. Angcw. C h m . Int. Ed., lY99, 38, 1468. ~
74% (96% ds)
Section 315 (Cwhoxylic Acid - h i d e ) Section 316 (Cuhoxylic Acid - Amine) Section 351 (Amine - Ester)
Related Methods:
SECTION 345: AMIDE - ETHER, EPOXIDE, THIOETHER
CI
2 ecl chirul Lewis acid i-Pr,NEt ,-2°C , 1 d
88% (83% ee)
Yoon, T.P.; MacMillan, D.W.C. .I. Am. Cherii. Soc., 2001, 123, 291 1.
H
2
N
e
C
1
0
,toluew
S% Dy(OTf)j ,4"C , 2 d G5% (92:8 endo:em)
Batev. K.A.; Powell, D.A.; Acton, A,; Ouugh, A.J. Tetruliedron Lett., 2001, 42, 7935.
OH
A~nide- Halide
Section 346
573
72%
Yl\ddv.; . . Reddy, B.V.S.;Pandey, S.K.; Siihaii, P.; Prathap, I. Tetruhedron Lett, 2001, 42, 9085.
0
2. Et0I-I ,NEt, ,reflux , 1 h
NHOH 0 CN Boukhris, S . ; Souizi. A . Tetulicdron Lett., 2000, 4 1 , 2559.
Prasad, B.A.B.;Sera, G.;
84~84% OEt
bx
m.V.K. TetrulicJdronLett., 2000, 41, 4677. MeTi(0i-Prh , ?HI;, it
37% (1:3 E:Z)
OBn
C,H,MgBr NB 112 Me Kordes, M.; Winsel, H.; De Meijere. 4.Eur. J. Org. Chenr., 2000, 3235.
A Nb0 A
EtSII , 10% IIf(0Tf)d 0°C 12% chiial oxamlidinone
;.s-
CI12c12, M S 4 A ,15 h
90% (67% ee) Ogawa, C.; Kawainura, M.; Sugiura, M. Synlett, 2000, 983.
-
SECTION 346: AMIDE HALIDE, SULFONATE
N-Ts
ItCl, , M&N , it 8.5 h
b h Y d . S . ; Subha Reddy, B.V.; Kuniar, G.M. Syizlett, 2001, 1417.
N HTs
574
Compendium of Organic Synthetic Methods, Vol 11
Kf
;-
1
.
.
;k'
TIIF, 30% Pd(PPh3)4, fluowscentPPh, light t
I
0
Section 346
0
N
I
TS
Isono, Y.; Iwamatsu, S.-i. J. Org. Cheni., 2001, 66, 315.
78%
Ts
90%
Bu4N (Ph,Si)difluorosilicate Ph
TI-IF , 0°C
NHSOxTol
Ph
L *L
Prakash. G.K.S.; Mandal, M.; Olah. G.A,Synlett, 2001, 77.
1. TsNCl2, MeCN ,r t , 22 h Pd(II)-( 1,lO-phenanthroline)
wC02Me *
Ph
2. 3 NaZSO,
Wei, H.-X.; Kim,S.H.;
Phm C O z M e
C02Me
Ph
1
81% (>95%1anti) Tctruhcdron, 2001, 57, 3869. 1. O-N~SNCIN~, MeCN 10% CU(0Tf)t
2.
COZMe
Ph
Na2S03
74% (>95: 1 anti:syn)
u; Wei, H.-X.; Kim, S.11. ?i,truhcdron, 2001, 57, 8407. 1. p , , W N l i 2
--+
80°C
NHSO 2P hEt
CH2CH2Ph
71%
; Steck, P.L. Eiir. J. Or#. Chem., 2001, 4353.
r
NHNS
. PhH, 18 h
MqAl/toluene , 0°C 2. 4 HCI , 0°C
10 nun
NHTS
I
s0,Ph
84%
Jones, A.D.; Wt.D.W. ; Mihhs, D.E. J. Chenn. Soc., I'erkin Trans. 1, 2001, 1182.
Section 346
A~nide- Hniide
A
+EtOH TMSCI,O°C+& ,1O%F&12 t
575
K
a
0
+&cl
NH
c1 9 ) 72%
(9 1 Dach. T.; Schluimner, B.; Ilarins, K. Clwii. Eur. J., 2001, 7, 2581.
A
Oxone, NaCI ,4S°C Wet N 2 0 , , 4 h
A/
* Ph
I 93% Ac .. UM.; Epifano, F.; Marcotullio, M.C.; Rosnti, 0.;Tsadjout, A. Synlett, 2000, 813. Ph
N HAc
cm,
Li, G.; Wei, 11.-X.; Kim, S.H. Or$. Lett., 2000, 2, 2249.
,
SOzMe
wtBEt,,02 , H 2 0 , 8 h
c
N-!B2Me
I Wakahayashi, K.; Yorirnitsu, €4.;Shinokuho, H.; Bull. Chein. Snc. Jpn.. 2000, 7.3, 2377. PMB
I
T
N
I
Mn2(CO),, , 0.11 M
-
DCM, hv
0
Gilbert, B.C.; Kalz, W.; Lindsay, C.I.; McGrail, P.T.; J. Chein. SOC., Perkin Truns. I , 2000, 1187.
77%
df 0
N
I
76%
PMB ; Whittaker, D.T.E.
Coinpendiuni of Organic Synthetic Methods, Vol 11
576
Section 347
BiCI12C02Et ,In ,THF
PhA N-Bn
8 O C , 12 h
0 Bn A.; Becker, F.F. J. Cheni. Soc., Perkin Truns. 1, 2000, 2179.
-Ghat&,
Rohin, S.; Rousseau. G. Eur. J . Org. Chwz., 2000, 3007. 1 . TsNCI2, MeCN ,MS 4,& 8% ZnC12
-COZMe Ph
2. Ni12S03
COzMe
Ph
85%
U;Wei, H.-X.; Kiln, S.H.; Neighhors, M. Org. Lett., 1999,1, 395.
&
NI-I2
i H T S
r 2O%NaOAc,NBS% ay McCN ,3.5h *
/
Naskar, D.; b v . S. J. Cticvn. Soc., Perkin Truns. 1, 1999,2435.
\ 46%
0
SECTION 347: AMIDE - KETONE
Q
y
1
Do
,reflux
0
M~CIICH2CHzONO
Rayaharapu, D.K.; Majumdw, K.K.; Samhaiah, T.; -P. J. Org. Chem., 2001, 66, 3646.
C.-
Section 347
h i d e - Ketone
0
PhI, K&03 , MeCN 5% Pd(pP11,)~,20 atm CO
c6H 13
90T,6 h
NIITs
* 3
TS
c6H
Kanp.;Kim, K.J. Org. Lett., 2001, 3 , 51 1 . QTIPS
6
577
I. CJI&IIO, MgSOi, It DCM , KZCO, 2. (Et02C)20 , EtOH , rt
Ts 57%
13
3. BF3*OEtz, DTBMP DCM , 0°C (317
72~87% (87% ee) Org. Lett., 2001, 3 , 1229.
Kanetani, A,;
w;
Frantz, D.E.; Soheili, A.; Tillyer, R.; Grahowski, E.J.J.; Reider, P.J. J. Am. Clzem. SOC., 2001, 123, 9696.
Ts s.
77% (26: 1 &ans:cis)
R.W- Satcharoen, V. Synlett, 2001, 532.
-A
10%~(MeCN)zPdCIz, DCM
1.5 t?q ChzNHz , 14 h Gaunt, M.J.;
1
org. L f r t . , 2001, 3, 2s.
NIICbz
84%
Compendium of Organic Synthetic Methods, Vol 11
578
a
MeO
NIITs SnCI, ,DCM , 5 h -78"C+
Section 347
* Me0
rt
73%
Ph . . Sllvelra.; Bemardi, C.R.; Braga, A.L.; Kaufman, T.S. Tetruhedron Lett., 2001, 42, 8947.
Hilgenkamp, R.; &rch er. C.K. Tctruhedrnn, 2001, 57, 8793.
6
1) 70%
(1
Clark.;Hodgson, P.B.; Goldsmith, M.D.; Street, L.J. J. Chem. SOC., Perkin Truns. I, 2001, 3312. PhCII=NTs McOI-I, 40"C, , 2 0 %1DMAP d
@'
50%
Shi.;Xu, Y.-M. Cherti. Cnrrrnrun., 2001, 1876
2.2 eq Bu3SnH ,AIBN toluene, heat
* O~ &sons.
A.F.; Williams, D.A.J. Tctruhcdron, 2000, 56, 7217.
58%
Anide - Ketone
Section 347
579
4Cm
Ti14 , MeCN, 0°C + rt , 22 h
Ph
Ph
MhcN-Bcx %: -
N -Ts . . Shlmlzu.; Sahara, T.; Hayakawa, R. Chein. Lett., 2001, 792.
NHTs
88%
Boc,
,EtzZn *
Me
Br
Br
toluene, 0°C
rt
Me
Paparin, J.-L.; Crkvisy, C.; Gr&. R . Tetruhedron LeJtt.,2U00, 41, 2343.
63% (92% bis-endo)
57% (955) ?MP
v
Alcdide.;Almendros, P.; Salgado, N.K. J. Org. Chetn., 2000, 65, 3310. Boc(Me)NCI-12SnBu3, CuCN
TIIF, 5 eq TMSCl
*
&
f"
N,
'6
; Alexander, C.W.; Nice, L.E. Tetruherlron, 2000, 56, 2767.
Me
98%
1. ' r M S ~ ' " "
Cr(C013
N-BZ
4. 3. 2.'IBAF h v PI1 ,02
\ *,st"\hP '
I
Ishimaru. K.; Kojima, T. J. C I Z P ~Soc., I . Pcrkin Truns. 1, 2000, 2105.
BZ 70% (80% de)
580
Compendium of Organic Synthetic Methods, Vol 11
Section 341
019 1) 92% ,vans P . L . Managan, T.; Rheingold, A.L. J. Am. Cheriz. Soc., 2000, 122, 11009.
* Ph H ZnBq , DCM H B t = benmtiizole 50% Katritzkv. A .R.;Fang, Y.; Silina, A. J . Org. Chcm., 1999, 64, 7622. Ph
Bt
03 OTMS
chiral nitiido-manganese (V)sale11 co1nplex
,,+"NIICOCF,
T F M , Py , E M , 6 h -78°C -., It
83% (75% ee)
Svenstrup, N.;BBgevig, A.; Hawll, R.G.; Joreensen. J. Chein. SOC.,Perkin Trans. 1, lY99, 1559.
I
sp
Ts Wane. .I. Hou, ; Y.; Wu, P. J. Clierri. Soc., Perkin Truns. I, I Y Y 9 , 2277. 1. CIjCCHO, NHzOII*HCI microwaves 2. IIzS04,mianwaves
52%
0
89~75% Janeshwara, G.K.; Bedekar, A.V.; Dcshpande. V.H, Synth. Coinitaim., Z999,29, 3627.
Aniide - Alkene
Section 349
581
SECTION 348: AMIDE - NITRILE NO ADDI'IIONAL EXAMPLES
-
SECTION 349: AMIDE ALKENE
-h. t-Bu
=
Me3Si
1,
O-Li+
[=N-Ts
, THF ,-7X"C 12 h
2. t-BuCIIO, -78°C
+
+
20°C
20°C , 6 h
\
Iwamoto, K.; Kojima, M.; Chatmi, N.; Murai. S . J. 0r.g. Chenz., 2001, 66, 169.
(74
26)
Ts
71%
89%
98:2cis:trur~s ' Jahin. I.; Revial, G.; Monnier-Benoit, N.; Netchita'ilo, P. J. Org. Chem., 2001, 66, 256.
0 N
I
1. f-BuLi 2. MqCu(CN)Li,
3. H 2 0
* W
N
H
T
r
s
71%
Tn Neipp, C.E.; Ilumphrey, J.M.; Martin. S.F. J. Org. Cherri., 2001, 66, 531.
Ph
Ph
. EG.; Trahocchi, A.; Guarna. A. J. Org. Chein., 2001, 66, 2459.
76%
Compendiuni of Organic Synthetic Methods, Vol 11
582
Section 349
-Br
Ph*N-SO,Ph
In
HZO
98% (39:61 syniunti) 95% (79:21 syniunri)
THF/€I,O
Lu, w.;
J. Org. Cheiii,, 2001, 66, 3467.
1. TiCb , DCM -7X"C-r -20°C
CO2Et
Ir
2. KIICO, 83%
Duncan, D.; Llvinphouse. T. .I. Org. Chem., 2001, 66, 5237.
99:1E:Z) IT,; Oya, S.; Murilkami, R.; Sntoo, Y.; Shishido, K. Tetruhedron Left., 2000, 41, 5947.
Section 349
589
Aniide - Alkene
MeO+OMeM e 0
1 . BuLi , LiCl , THF ,-78°C
p i-Pr
67% (67%ee)
3. HCI, rim, OT IIarrington, P.E.; Tius. M.A. Org. Lztt., 2000, 2, 2447.
Bz"-P I
-
LDA ,TIIF-IIMPA
Bn
SiMe,Ph
Anderson.;Flaherty,
-78°C
-f
SiMe,Ph
40°C
84% (20: 1 ) A.; Swarhrick, M.E. J. O r g . Chent., 2000, 65, 9152.
\
* yLj(O?'f)3, air, TIIF
+
-J (65
Porter. N.A.; Zhang, G.; Reed, A.D. Tetruhedr-onLftt., 2000, 41, 5773.
35) 82%
\
w;
Bn
89%
I'retwell, P.; Sansuno, J.M.; Sridharan, V.; Sukirthalingm. S.; Wilson, 11.; Redpath, J . Tetruhrrlron, 2000, 56, 7525.
Section 349
Compendium of Organic Synthetic Methods, Vol 11
590
4 eq MeCu(CN)Li=LiBi*2 Li
I
MTS
Me
MTS = 2,4,6-timethyhenzenesulfonyl
93% Ohno, H.; Toda, A.; Miwa, Y.; Taga, T.; Fujii, N.; Ihuka. T. Tetruhedron Len.,1999, 40, 349.
&\J
u Lh
do [Pd(MeCN),I[BFJ,, CH2CI2,72 h
fi
Ar,
71% (83% ee)
AI = 4-CF3 phellyl Jiang, Y.; Longmire, J.M.; 7,hane. y Teriohedron Left., ZYYY, 40, 1449.
r-BuMqSiCl195"C111 12 h C O , RhZ(C0)12, Ph€I
B-u
4rD SiMe,t-Bu
* Bu
pyrrolidine
90% (9?:3 Z E )
0
Matsuda. I.; Takeuchi, K.; Itoh, K. Tetruhodron Lett., ZYYY, 40, 2553
A
r
-
5% Pd feimcenyl oxazoline CH~C12,23"C, 3 d
3
C3H7
.
Donde, Y.;
J. Ain. Cheiil. SOC.,ZYYY, 121, 2033.
67% (91% e e , R)
1. (-)-sparteine, BuLi toluene, 1 h
N &'
\B
*'
,HzO
/
cH2(CNh
\
CN
ce tyltrine thylammonium 0 2 b chloride
. . Balllnl.; Bosica,
G.; Conforti, M.L.; Maggi, R.; Mazzacani, A,; Righi, P.; Sartori, G.
Tctruliedron, 2001, 57, 1395.
1. 10% SC(R-BINOL)~L~ ,TMSCN
*
toluene, -2O"C, 9 11 ph>N-Bn
F%qNIl13n
2. H20
>95% (88% ee) Chavarot, M.; Byrne, J.J.; Chavant, P.Y.; VallCe. Y, Tetruhcdron Asymm., 2001, 12, 1147.
0m
F%
/J
Bu,SnCN, 0.1 ZifOt-Bu), 0.3 R-6-Br-BINOL , 12 h toluene , PhH, -65°C
-
0°C
1
92%(91%ee)
Ph
CN
Ishitani, H.; Komiyama, S.; IIasegawa, Y.; Bohavas,hi. S . J. An1. Chent. SOC.,2000, 122, 762.
i-PrCHO
PhNIIOH , MqSiCN ,rt 5M LiClO, , ether 15 min
-
/INP
i-19
I OH
WA.: Lavijani, 11.; Emami, J.; Kararni, B. Tetruliedron k t t . , 2000, 41, 2471.
97%
2
ma r
Compendium of Organic Synthetic Methods, Vol 11
610
NC
CH2=CHCN*MeCN hv (254 nm) ,rt
* a +
t
Section 356
"+.
Bn-N 52%
Ishii.;Shimada, Y.; Sugiyama, S.; Noji, M.J.
26% Chetu. Snc., Pcrkin Truns. I, 2000, 3022.
*x
10% chiril Schiff base, bluene 10%Ti(0i-Pr), ,2 eq TMSCN
AN , C m
Ph
CN
82% (>99% ee)
1.5 i-PiOH (add over 210 h)
Ph NHCHPhz Krueger, C.A.; Kuntz, K.W.; Dzierha, C.D.; Wirschun, W.G.; Gleason, J.D.; Snapper, M.L.; J. Am. Chcni. Sac., 1999, 121, 4284.
N-CHPh2
NHCHPh,
N
H
2. HCN , 0 . 2 M in toluene -4O"C, 20 h
Ph
*
IIIII
H
Ph 96% (86% ee)
Corev.; Grogan, M.J. Oi-g, Left., 1999, I , 157.
-
SECTION 356: AMINE ALKENE
Ph 2eq Ph-Et , 100°C 5% Pd(OAch, LiCl, 36 h i-Pr2NEt, Bu,NCl
Roesch, K.R.;
Et
J. Org. Chem., 2001, 66, 412.
mNrnoc PhOTf , Pd(OAc)z, dppf MtCN , KzCO3, 9@l°C
*
N ,(H )F3oc Ph
70% Olofsson, K.; Sahlin, H.; Larhed, M.; J-lnllher~ A. .I. Org. Chetn., 2001, 66, 544.
75%
Section 356
61 1
Amine - Alkene
>95%
Blackhum, L.; Tavlor. R .J.YOrg. Lett., 2001, 3 , 1637.
1
-
Bu,
N/
t-Bu
30% CuI,NEt3 DMA , 110°C
4
Bu
t
86%
I
t-B u Kel'in, A.; Srornek, A.W.; Gevorevan. V. J. Am. Cheni. Soc., 2001, 123, 2074. Ph
0-rnentiyl
I
COC)&r
.!
C6H13
pph3
D; Yu, C.-W.;
2
Ph
Section 360
,MeOH, acebne It
-u 0
82%
Yuen, W.-H.; Yang, D. J. Org. Chem., 2001, 66, 3606. -78°C ,CHzClz
_(OTBS
i
-
k
ui-pr (t-Bu)S
88%, 79% II 0 Harada.;Iwai, H.; Yakatsuki, €1.; Fujita, K.; Kuho, M.; Oku, A. Org. Lett., 2001, 3, 2101. S(t-Bu)
9
BIC13zC0zMe, PhH AIBN ,80"C, 4 h Miura, K.;Fukisawa, N.; Saito, H.; Wang, D.;
ph 86% Org. Lett., 2001, 3, 2591.
*
1. EtzZnCHzI 2. cat TMSCl
Me 0
Hilgenkamp, R.;Tercher. C.Y, Org. Lett., 2001, 3, 3037. &COZEt Ph
Ac@ , MgJDMF +
TMSCl
63%
Ph
64% COZEt
flazcy:\
Ohno, T.; Sakai, M.; Ishino, Y.; Shihata, T.; Maekawa, H.; &d&&LL Org. Lett., 2001, 3, 3439.
-
1.2.5 eq TMSCl, THF 2.4.5 -78°C eq S d z ,-10°C THF *@rZc6H13
Me-
N Ph
3 . 4 eq IIMPA 4.1120
McDonald.;Galka, A.M.; Green, A.I.; Keane, J.M.; Kowalchick, J.E.; Micklitsch, C.M.; Wisnoski, D.D. Tetruliedron Lett., 2001, 42, 163.
Ester - Ketone
Section 360
627
2 eq IZn(CHz),C02Et1 20°C 7'IIFJtolueneJDMF , 2 2 h
* L
1.5% P d S
C7H15
C
C7H15
0
PhI(0Ach ,TsOH
O
T
s
~
&:
t
Ph+rs
microwaves, 99% Wilkinson, H.S.; Grover, P.T.; Vanddenbossche, C.P.; Bakale, R.P.; Bhongle, N.N.; Wald, S.A.; Senanavake. C.H. Org. Lztt., 2001, 3, 553. 0
Section 362
Compendium of Organic Synthetic Methods, Vol 11
630
Dcc
98% ds)
Villar, P.; Equey, 0.;Penaud. P. Org. lxtt., 2000, 2, 1061.
OMe Yadav. J.S,; Reddy, B.V.S.; Hashim, S.R. J. Chern. SOC.,Perkin Truns. 1, 2000, 3082.
Section 364
Compendium of Organic Synthetic Methods, Vol 11
642
PhCHO
Mn/TMSCIICpzTiC1,,THF
*
Phq
P
0°C. 1 d Dunlap, M.S.;
SECTION 364:
O -H Yang, X.-F.; Mague, J.T.;
Synth. Conunun., 1999, 29, 1097.
b
oms
73% (13:l dr)
-
ETHER, EPOXIDE, THIOETHER HALIDE, SULFONATE
PhCHO ,InC13, DCM + It ,overnight
(>, @@\
u.C . J . J. Org. Chem., 2001, 66, 739.
Ph
85%
Gomtsvan. A,; Koenig, R.J.; Lee, C.-H. J. Org. Chem., 2001, 66, 3613.
BF,.OEt,, AcOH 61%
hexane ,-78°C Jaher, J.J.; Mitsui, K.; w v s k v . S.D. J. Org. Chem., 2001, 66, 4679.
1-0
Me0 Me0 b v . S.C.; Guin, C.; Rana, K.K.; Maiti, G . Synlett, 2001, 226.
87%
Ether - Halide
Section 364
Li, J.;
643
95% (3: 1 cis:trans)
u.C . 4 , Tetruhedron Lett., 2001, 42, 793.
Albert, S.; Robin, S.; Bousseau. G , Tetruhedron Lett., 2001, 42, 2417.
Br
Talyhov, G.M.; Mekhtieva, V.Z.; Karaev, S.F. Run. J. Org. Chem., 2001, 37, 600. 0 $% .%
QSiC13 -
SiCl, , i-Pr,NEt CHZClz, -85°C
---
fiB
&h
* Ph
5% fluorinatedarene ligand
Ph
88% (94% ee)
--
C1
Tao, B.; Lo, M.M.-C.; Fu. G.C. J. Ant. Cheni. Soc., 2001, 123, 353. OSiMe3 Bn-NnN+CF3 - H ph
Ph
+
10%CsF, 0°C , glyme, 5h
86% CF3
; Blond, G . Tetruhedron Lett., 2000, 41, 8777.
-013
NaIO, / NdI SO3
Okimoto, Y.; Kikuchi, D.; Sakaguchi, S.;
MeCN
-06
% I
61%
Tetruhedron h t t . , 2000, 41, 10223.
Section 365
Compendium of Organic Synthetic Methods, Vol 11
644
MeOH , dioxane, rt ,0.75 I2
0.25 C e ( 0 T G
O
l %' ##
M
Y
~ Z X J LShekarriz, ; M. Tetruhedron Lett., 2000, 56, 5209.
L
P hCI I 0 ,IIIC13
-
APh 81%
PI1 Ph Yang, J.; Viswanathan, G.S.; Li. C-L Tetruhedron Lett., 1999, 40, 1627. Et,NSiMe, , 2 eq Me1 80-90°C , 5 h ; Yamamoto, Y.; Matui, C.
Ohshita, J.; Iwata, A,; Kanetani, F.; J. Org. Chern., 1999, 64, 8024.
81%
SECTION 365: ETHER, EPOXIDE, THIOETHER - KETONE
6'
"
tlco
e
+
R
, cat TMSOTf
0
MtCN , -30°C
-
rt , 10 min
* &SMe
94%
Matsugi, M.; Murata, K.; Gotianda, K.; Nambu, H.; Anilkumar, G.; Matsumoto, K.; U t a . J. Org. Chem., 2001, 66, 2434.
pms f
1. c3rr+xo,
Y.
M ~ S Ort~ ,
2. (EtOzCkO, EtOII , rt 3. BF3.OEt2, DTBMP EtO,C/ DCM ,0°C
C ,€I, Cohen, F.; MacMillan, D.W.C.;
7 2 ~ 8 7 %(87% ee)
; Romero, D. Org. Lett., ZOOZ, 3, 1225.
Section 365
Ether - Ketone
645
-4
PhSH , TIIF, LiAl-ply2a 30 min
-G;. 7
SPh
Prahagaran, N. Org. Left., 2001, 3, 389.
.
95% (41% ee)
APh
chiral phase transfer agent, PhMe
Ph
*PhA
aqNaOCl,lt
P 98% (86% ee)
Lvea.;To, D.C.M. Trtruhedron Ixtt., 2001, 42, 1343.
=+ OEt
OEt
-kPh OEt
=(OTMS Ph
1% Sc(OTfb
*
m a t s u . M.; Kurihayashi, M.; Koike, T. Synlett, 200Z, 1799.
Schmitt, A.; &&igJJ-
-
J
h
Eur. J. Org. Chan., 2001, 1169.
'\
1. MeOTf, DCM ,0"C 2,6-di-t-Bu-Py . aq N a H 0 3
*
57%
0
86% (61:39 kznscb)
'p
-A.;Draffen, A.G. J. Chem. Soc., Pmkin Truns. I, 2001, 2861.
81%
Compendium of Organic Synthetic Methods, Vol 11
646
1. 0
Section 365
2 ,Mn(Q abietate PhH, rt
Ph
0
Kulinkovlch.;Astashko, D.A.; Tyvorskii, V.I.; Ilyina, N.A. Synthesis, 2001, 1453.
TS
1. BCl3 , DCM , -78°C
Ph
2. pH 7 buffer
E
OMOM
H
n.,,E
Gasparski, C.M.; Hemnton, P.M.; Overma Tetrahedron Lett., 2000, 41, 943 1.
.
85%
+-)
.; Wolfe, J.P.
Ph
1. m ~ o H B F 3 - o ~
8 5 T ,90 nun
P hCH,C 0,H
* Ph
2. BF3eOEt2, DMFPCls rt,lh Balasuhramanian, S.;
L
Hollmann, C.; &&r&t&
Synth. Commun., 2000, 30, 469.
CO/II2 (80 bar) ,W"C, 2 d [Rh(cod)Cl]z, DCM
-
0
80%
GS
64% (1:l dr)
Tetruhedron, 2000, 56, 1685.
CAN ,MeOH , rt
n \
Ph
flair. V.; Nair, L.G.; Panicker, S.B.; Sheeha, V.; Augustine, A. Chem. Lett., 2000, 584.
5% Sc(OTf)3 , 10%Me011
,-),
..
\ /
/
N,
CHza2
Jain, R.P.; Bhattacharyya, A. Tetruhedron Lett., Z999,40, 5255.
OMe
647
Ether - Nitrile
Section 366
A
COzEt
COzEt
Br
2. K2C0,, acetone, rt
65~75%
0
n. P,V,; Krzeminski, M.P. Tetruhedron Lrtt., 1999, 40, 7879. Me&( OMe)SPh SnCl,
;-
* O M *.
62%
with TiCI4, RSPh is obtained in 86% Dronelles, L.; Silveira, C.C.; Wessjohann, L.A. Synthesis, 1999, 562.
. .
A
aJp,, CHO
, LiOH-H@
10%chiral phase transfer agent Bu,O, 4"C, 60 h
Arai.;Shirai, Y.; Ishida, T.;
e
P
h 80% (53% ee)
Tetrahedron, 1999, 55, 6375.
REVIEWS: "Epoxy Ketones as Versatile Building Blocks in Organic Synthesis," Lauret.C. Tetruhcdron Asynini., 2001, 12, 2359.
SECTION 366: ETHER, EPOXIDE, THIOETHER - NITRILE 10% Ti coinpkx, TMSCN
THF ,-5°C , 3 6 h 88% (76%ee) IIamashima, Y.; Kanai, M.;
'
Tetruhedron Lctt., 2001, 42, 691.
Lo*.
TMS-CN , h B r 3 ,CHzClz i
Ph
rt,3h
L Ph
O
A
c
CN 97% Bnndini, M.; Cozzi. P ,G; Melchione, P.; Umani-Ronchi. A. Tetruhedron Lctt., 200Z, 42, 2041.
648
Compendium of Organic Synthetic Methods, Vol 11
Section 366
-x
his-Ti-sakn complex (0.5%) MqSiCN,DCM,ld
A
Ph quant (66% ee) Ph CN Belokon, Y.N.; Green, B.; Ikonnikov, N.S.; North. M,; Persons, T.; Tararov, V.I. Tctruherlron,2001, 57, 771.
1. [DCM , EtZAlCl, rt , 2 h whohydrate phosphine oxide ligand]
PhCI10
-78°C 2. TMSCN , -60°C Kanai, M.; Hamashima, Y.;
96% (80% e e , S)
* Ph1 : N
>yny) '
Tetruhcdron Lett., 2000, 41, 2405.
Do
N
N
b '.
Th4SCN ,CIIc13 , -45"C,Ph 4 d * u , ( 9 1% ,% , e e )
Schaus, S.E.; Jacohsen. E& Org. Lett., 2000, 2, 1001.
A
TMSCN , 10% Ti(0i-Pr), , THF
K
TMSO,
-
10% chiral phosphine oxide Ph 85% (92% ee) -30"C, 36 h ' Hamashima, Y.; Kanai, M.; J. Am. Chem. Soc., 2000, 122, 7412. Ph
n
PhCIIO ,phase transfer catalyst NaOH
Makosza.; Pr.yborowski, J.;
d,
+q 0
Klajn, K.;Kwast, A. Synlett, 2000, 1773.
SePh
,,,,*I>*'
CI12=CIICN, Bu,SnII N B N , PhH , heat
I1IIIIl)
0
z
P
8
0
C02Me
Nimkar, K.S.;
-dfi 46% (2.1: 1 trunsxis)
cN
C1
--i
53% CO2Me Tetrulieclron,2000, 56, 5793.
+
CN
8
4 15%
C02Me
CN
Section 366
Ether - Nitrile
0
PhwcN 1. - 0 K O E I 10 eq\-(-)H
CN
Xie, R.L.;
5% Pd(PPh,), ,rt , Id 2.5%Gruhhs' catalyst, DCM CH,=CH, atmosphere, 1*d
649
ph6 81 X94%
Hauske.J.R.Tetruhedron Lett., 2000, 41, 10167.
N
M4SiCN , 3 M LiQO,/ether
Jinur.&
_".. ,
0.1 mPa
Ph
98%
Tetruheclrnn Lett., Z999, 40, 491.
TMSCN
0.1%chird Ti (salen) complex PhCHO
YTMS
86% ee
%,,,
CHzC12,rt , 1 d
Ph CN Belokon', Y.N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N.S.; Khrustalev, V.N.; Larichev, V.S.; Moscalenko, M.A.; North.; Orizu, C.; Tararov, V.I.; Tasinazzo, M.; Timofeeva, (3.1.; Yashkina, L.V. J. Am. Chetn. Snc., 1999, 121, 3968.
Testafeiri, L.; Santi, C. Eur. J. 0 1 - g . Chem., 1999, 797.
;-
PhCIIO
TMSCN ,Zr(Kpo,)z, DCM
90%
XO~S
reflux * 98% Ph Curini. M.; Epifano, F.; Marcotullio, M.C.; Rosati, 0.; Rossi, M. Synlett, Z999, 315. M q S i C N , 1d
b
1% chiral Ti salen complex
Ph Belokon. Y.N.; Green, B.; Ikonnikov, N.S.; Porth. M.; Tarapov, V.I. Tetruhcdron LEtt., 1999, 40, 8147.
quant (62% ee)
650
Section 367
Compendium of Organic Synthetic Methods, Vol 11
SECTION 367:
phx -
ETHER, EPOXIDE, THIOETHER ALKENE
Enol ethers are found in this section as well as alkenyl ethers.
EtOzC
C0,Et
Y,
PhI, 25°C , THF ,0.25 h InULYHCRCCHZOH]
[5% PdClz(PPh3)@uLi]
-
COzEt
89%
Bottex, M.; Cavicchioli, M.; Hartmann, B.; Monteiro, N.; J. Org. Chem., 2001, 66, 175.
MC7""
B IIOH, 5 % Pd(PPh3)4 10%P(O-TOl)s ,THF
&
100°C,3 d
0
Ph
noT
Ph
C7H15
69% Y. J. Org. Chem., 2001, 66, 270.
H Camacho, D.H.; Nakamura, I.; Saito, S.; -to.
3. E $AcOII 2 ,Pd(0Ac)Z*
& o
& m e c o e c h e a . ; Pkrez, E.; Solay, M. J. Org. Chem., 2001, 66, 564.
I n , H,O--EtOII ,rcflux
-
* pho40 h Ranu.; Dutta, J.; Guchhait, S.K. J. Org. Chem., 2001, 66, 5624. /
OH
90%
,Id
a t Pdz(dha)3
Lahmsse, J.-R.; Lhoste, P.; ~
O
U
D,. J. Org. Chetn., 2001, 66, 6634.
chiral pyrmlidho-oxazolidine PhOTf , PhH , Pdz(dha)3 i-PrzNEt, 75°C , 3 d
S . k ; Xie, D.; Fu, 2. J. Org. Chem., 2001, 66, 7240.
85% conversion (82% ee)
Ether - A k e n e
Section 367
65 1
(CII,=CH)*Sn ,Cu(0Ach * P 0, , M e C N , r t , 2 2 h Blouin. M, ; Frenette, R. J. Org. Chem., 2001, 66, 9043.
h
e
\ /
O
7 93%
oom ,chiral P,N-ligand
Pd$dha)3 ,i-Pr2NEt, PhH 70"C, 22 h
t
Gilhertson. S.R; Ru, Z. Org. Lett., 2001, 3, 161.
Bu,NEir, BSA
+
-
~~
105"C, 4 h
%
quant (94%ee)
B SA = (his-trimethylsily1)acetamide
10) 90%
(90
Smietana, M.; Mioskowski. C. Org. Lett., 2001, 3, 1037.
.
Gruhbs' oltalvst PhH
.&I
1.
M.-P,; Baylon, C.; Nolan, S.P.;
'
Org. Lett., 2001, 3, 1989.
10% AgC13
Me
014 IIoffmann-Riider, A,;
Org. Lett., 2001,3, 2537.
Br
Lee.;Lee, K.; Kim, S. Urg. Lett., 2001, 3, 3205.
74%
65 2
Compendium of Organic Synthetic Methods, Vol 11
Section 367
C02Me
Me0
A&.
DCM Tic& , -30°C , 3 h SiI’h2tBu
* & @ :$% 69e
ButP h2Si
Yadav.;Balanuragan, R. Org. Lett., 2001, 3 , 2717. 1.
PhCHO
mlO2s
/=Iy2
, DMAD, 25°C
*
42%
2. NEt3 , 6 5 T
lohnson.; Cheshire, D.R.; Stocks, M.J.; Thurston, V.T. Synbtt, 2001, 646.
c,ri 1 7 , (3rci2 ~ ,H,O ~ MqSiCl ,THF ,25”C, 1 d -
L
P
~
*
h
. K.:Morita, R.; Sakiunoto, S. Synlett, 2001,
*
1614.
1. Ph2CIIO€I, LIIMDS THF ,-78°C
Phozs -so2F’h
Ph
80%
+
2. Na/Hg, NaH2P04, M&II
Ph,rrco
A \
93% Cahianca, E.; Chkry, F.; pollin. P,; Cossu, S.; Pe Lucchi. 0. Synlett, 2001, 1962.
kx 0
OMe
C€12=€IIOEt , MgBr2=OEt2 ether, it, 15 min
*
d
0
O
E 90%
Mannucci, S. Tetrahedron L.ett., 2001, 42, 2023.
;-
2 qi-Bu3Al , DCE , 5 h
*Lp
Ph Cahrera, G.; Fiaschi, R.; Napolitano. E. Tetrahedron Lett., 2001, 42, 5867.
Ph
=
Me
BnOH , 10%P C I ( P P ~ ~ ) ~ 10% PhCOJ-I, dioxane , 100°C
Kadota, I.; Lutete, L.M.; Shibuya, A,; -to.
t
*
Ph
78%
OBn 96%
Y.Tetrahedron Lett., 2001, 42, 6207.
Ether - Alkene
Section 367
653
3. PhI, cat Pd(PPh3)4 NEt3 ,60"C
. & .; 011 -
-
Perez, E. Tetruheron Lett., 2001, 42, 3839.
p
-
COzMe
a t Pd(MtCN)2ClZ
-0 I
O
O"C, 0.5 h
o C O z M e
,."'
95%
T
C02Me
Kato. K.; Nishimura, A,; Yamamoto, Y.; Akita. H. Tetruhedron Lett., 2001, 42, 4203.
- -
-1
0.5 YhSeSePh , 3 h NaBHdEtOII ,reffux
C6l113
PhSe
c61I13
; Baroni, A.C.M.; LenardSo, E.J.; Gianeti, T.R.; IIurtado, G.R. Tetrulzerlron, 2001, 57, 4271.
4C0zMe
''
DABCO , 1 1 2 0 , rt , 2 h Kavichandran. S. Synth. Commun., 2001, 31, 1233.
COzEt
PhS
Cp2T4P(OEt3]z1 2 h reflux
Ph
+
P
h
a p e
d 62%
-ao
Rahim, Md.A.; Sasaki, H.; Saito, J.; Fujiwara, T.; T a k e d a . C h e m . Commun., 2001, 625.
A
1. LiC-KOR , T I I F , -95°C 2. B B u ~, 4 5 " C
3. HzO , -95°C OEt Tivola, P.B.; Deagostino, A.; M.C.: V-
86%
Clzern. Commun., 2001, 1536.
654
Compendium of Organic Synthetic Methods, Vol 11
4 PI1
Section 367
,Mn(OAc), , 4 0 T
[bmim] BF4, DCM
OH Bar, G.;
; Thomas, C.B. Chem. Cornmun., 2001, 1350.
50%
1. PhCCH , 2 eq MeMgCl 2. cat Pd(PPh3)2C12
Chaplin, J.II.;
B.L. Cltern. Cornmun., 2001, 1594.
1. PhCI-I=CH2,TiC14, DCM
2. KOII , rIZo
65% (1 :1 cis:trans) Kervredo, S.; Loiseau, M.; Lizzani-Cuvelier, L.; Duiiach. E. Chem. Commun., 2001, 2284. SiMqPh HSiMe2Ph , 3 % Pt complex 3% Py , S O T , 9 h W' .; Yamamoto, S.; Kawagishi, S.; Hiraoka, M.; Ikeda, S.; Minami, T.; Ito, S.; Yoshifuji, M. Chcm. Lett., 2001, 972.
Bu
2% Pd(PPh,), , 5 h * 4% P(OBu), 1. V.K.; Alonso, E.; Hynd, G . ; Lydon, K.M.; Palmer, M.J.; Porcelloni, M.; Studley, J.R. Angrw. Chem. In?. Ed., 2001, 40, 1430. 0
Ether - Alkene
Section 367
K
MQCO
t
H
u
5% [Pd~(dha)~].CHCl~ , 2h 20% dppe ,dioxane ,50°C
655
'0'0,
&If
OMe
85 %
Angew. Chern. In.t. Ed.,2001, 40,616.
Yoshida, M.;
s; Ishiwata, A.; Suzuki, T. Bull. Chern. SOC. Jpn., 2001, 74, 569.
uoB OTMSOTMS
-
92'4Tcb
E M , MS 4A,-78°C
20°F
COZEt
w; Eckardt, T. Angew. Chern. Int. Ed., 2000, 39,4343. K
70% (>98:2 EtZ)
1. CkZ,r(H)Q ,THF ,rt , 3 0 min 2. Se ,I.t, 30 min
=
72%
3. B a r , 5OoC, 1 h Hunnp.;Wang, J.-I-I. Synth. Cornniun., 2000, 30,307.
P h =
l.ZICp2(H)CI,DCM
L
Ph
*
2. PhzTez Liang, C.-G. Synth. Comr,zun., 2000, 30, 1737.
'OZEt
Se-Bn
ph*
TePh
67%
EtO,C BnCIIzCl.CH, toluene
CuI , DBU , aqTHF
Ph
hrcadl.; Cerichelli, G.; Chiuini, M.; De Giuseppe, S.; Marinelli, F. Tetruhedron Lett., 2000, 41,9195.
91% 0
656
Compendium of Organic Synthetic Methods, Vol 11
Section 367
MiGS.; Gao, W. Tetruhedron Lett., 2000, 41, 8933
Gogonas, E.P.; Uadiiaranodou. L.P. Tetruhedron Lett., 2000, 41, 9299.
e. r\L; I ~ u x M.; , Hoffmann-Roder, A. Tetruhedron Lett., 2000, 41, 9613.
2 eq M e 3 k C H C N , toluene
PhCOZMe
100"C,2d
Nan, Y.;Miao, 11.;
Org. Lett., 2000, 2 , 297.
Ph
HCtCCHzOH , THF Pd(PPh3hCb , t-BuOK reflux
Ph Monteiro, N.; Balmc, G . J. Org. Chem., 2000, 65, 3223.
MtO
CN
Section 367
T
M
657
Ether - Alkene
s
4 V
i-Bu
O
SnBu,
2.1 Ce(NB~4)2(N03)6,25°C* MeCN-DCM, MS 4A
yo 88%
i-B u
Chen, C.; M ~ ~ L J L J.&Org. Chem., 2000, 65, 3252.
Younr.;Jung, L-j.; Cheng, K.-m. Tetruhedron Lett., 2000, 42, 3411.
Pale.;Chuche, J. Eur. J.
Org. Chent., 2000, 1019.
LiCl , Pd( PP h3)4
Ph
N
75%
Schaus, J.V.; Panek. J.S. Org. Lett., 2000, 2, 469. Ph-
99
Et
0
e- , Et,NI, NEt,-THF CHlCl2, rt
e
Kobayashi, S.; Sawaguchi, M.; Ayuha, S.; Fukuhara, T.;
PhCHO
1) 95%
0;
Oiappe. C.; Capraro, D.; Conte, V.; Pieraccini, D. Org. Lett., 200Z, 3, 1061.
90%
,* .
Synlett, 2001, 1938.
PhCH=CHZ, BC13 , CHZCl2 Phu
p
h
9wo (53:47RR(SS):RS(SR) Kahalka. G.W.; Wu, Z.; Hu, Y. Tetruhedron Zxtt., 2001, 42, 5793.
CAN, KBr , H z 0 , DCM rt ,20min
BuyB
Br Nalr.;Panicker, S.B.; Augustine, A.; George, T.G.; Thomas, S . ; Vairamani, M. Tetruherlron, 2001, 57, 7417.
82%
Section 371
Halide - Alkene
SECTION 369:
663
HALIDE, SULFONATE - KETONE
Yorimitsu, H.; Shinokuho, €1.; Matsuhara, S.; J. Org. Chem., 2001, 66, 7776.
; Omoto, K.;
6 e q K g 0 3 , S e q B r 2* u
r
+
0°C , 5 h
I&
97%
Zhang, W.-C.; Li. C.-J, J. Org. Chem., 2000, 65, 5831. 1. LDA, TfIF 2.TsCl
Ph
*
Ph
a
61%
Brummond.,Gesenherg, K.D. Tetruhedron Lett., 1999, 40, 2231.
A
Ph
1. IIMB ,MeCN ,reflux 2. SiiIT2,THF ,rt
* PhL
I
82%
HNIB = (hydroxy-p-nitrobenznesulfony1oxy)benune Lee. J.C.; Jin, Y.S. Synth. Cornmun., 1999, 2Y, 2769.
SECTION 370:
-
HALIDE, SULFONATE NITRILE NO ADDITIONAL EXAMPLES
SECTION 371:
Bu
Dahdo
=
HALIDE, SULFONATE - ALKENE
SnBu3
1. CpzZr(H)CI ,THF ,rt 2.2.15 eq I2 , TfIF ,rt
*
BuH1 78%
H
I
I ; Dahdouh, V.B.; Baroni, A.C.M. J. Am. Chem. Soc., 2001, 123, 9694.
664
Compendium of Organic Synthetic Methods, Vol 11
Section 371
C7H15
OAC
1.5% Pd(OAc)z , 4 0 T 2.5 eq LiBr , AcOH , 25 h acetone
Horviith, A.;
-
J. Org. Chem., 2001, 66, 8120.
+lJ
C5H1 1
85 %
SWe3 1.2.5 eq CPZzZr(WC1
ITIF, 53°C 2.12 , DCM ,It
3. MeZnCl , Pd(PPh,)4-THF 4.12 ,DCM Arefolov, A,; Langille, N.F.;
50~95~75%
Org. Lett., 2001, 3, 3281. 1. Zn,DMAC
F Liu, Q.;
Ph
2.PhI,CuBr,rt Ir cat Pd(PPh3)4 , 4 h DMAC Tetrulzedron Lett., 2000, 41, 8045.
A/
Ph
76 X 74%
AccC1 , ZnClz/SiOz ,DCE
3 0 T ,1 h
-+
PhL
M
e
91%
KKodomari. M.; Nagaoka, T.; Furusawa, Y. Tetrahedron k i t . , 2001, 42, 3105.
Bu
=
Su, M.; Yu, W.;
SPh
TMSBr ,CH2Q2, -40°C MaH,1h
- Buq-sph
Tetruhedron Lxtt., 2001, 42, 3771.
NBS , K-10 Monhnorillonite MeOH
99%
Br
Br 60%
665
Halide - Alkene
Section 371
V.G : Balenkova, E.S. Synthesis, 2001, 2081
Shastin, A.V.; Korotchenko, N.; =nko.
K:
AczO , MgBq ,T H F
CqMe Ph+
*
It,lh
Ph
86% (100%Z)
handran . S.; Synth. Corrlnzun, 2001, 31, 2059.
M
cetylMe,NBr, DCM , KzCO3 0°C-
It
=
Chem. h t t . , 2001, 290.
Bose, G.; Barua, P.M.B.; Chaudhuri, M.K.; Kalita, D.;
Bu
NCS
*
70%
&Br
&Bu
Br 82%
IIoshl.;Shirakawa, K. Tetruhedron Lett., 2000, 41, 2595. 1. CCI3COzII, Cl3COzNa DMF ,35"C
2. AcZO, 25°C 3. Zn , AcOM ,6O"C 92% C1 Wane.;Campagna, S.; Xu, G.; Pierce, M.E.; Fortunak, J.M.; Confalone, P.N. Tetruhedron Lett., 2000, 41, 4007. CHCb ,6O"C, 34 h BF4;.T-
. .
/-/I
Fujita, M.; Gronheid, R . ; Lodder, G. Tetruhedron I L K , 2000, 41, 5125.
93%
666
Compendium of Organic Synthetic Methods, Vol 11
95% (42% ee)
1. C02(CO), MS 4A , -10°C ,toluene * Br 2. TMANO
Br
90%
PCrez-Serrano, L.; Casarruhios, I..; Dominguez, G.; --Cast-
Synlett, 1999,587.
Ishizaki, M.; Iwahara, K.; Kyoumura, K.;
KTrn
0
Org. k t t . , 1999,1, 1187.
p 2 ( ~ ) ,
3.5 eq PhSMe , DCE 83"C, 10 min
;-
.
;
,
Yamada, M.;
@ /
'
; Nishizawa, M. Synlett, 1999,771.
4 eq4 CoF3 e q € I z, 0dioxane ,rt ,rt
/
OMe Tomatsu, A.; Takemura, S.; IIashimoto, K.;
-
@ / 0 Synlett, 1999, 1474.
87%
Section 376
Nitrile - Alkene
689
-
SECTION 375:
NITRILE NITRILE
/"
PBu3 ,300mPa, 50"C, 1 d
quant (77:23 trum:cis)
Jenner. G. Tetruhedron k t t . , 2000, 41, 3091.
-
SECTION 376:
NITRILE ALKENE
8-6
COzMe
COzMe
40%
Chavan.;Shrma, A.K.; Ethiraj, K.S. Synlett, 2001, 857.
=
Me
NEtz
MqSiCN ,DCM ,20"C
M q s i . c N NEtz
59%
15 h Me . N.V.; Kazantsev, A.V.; Borisenko, A.A.; Beletskaya, I.P. Tetruhedron, 2001, 57, 10309.
/x
"m,,,cat Bu4N HS04
50% aq NaOH, cyclohexane ether, 55"C, 5 5 h BA.; ,. Gierczak, A.H. Synthesis, 2001, 93. Ph
PhCI I 0
*
ba 71%
Ph
CIIz(CN),,NaZCO,,MS4A
*
,qCN
97% CN Siehenhaar. B.; Casagrande, B.; Studer, M.; Blaser, H.-U. Cun. J. Chem., 2001, 79,566. 70°C
PhCHO
CHZ(CNk ,TEBA , neat
Best., .. Narsaiah, A.V. J. Chem. Rex (S), 2001, 36.
* PhCH=C(CNk
88%
Section 376
Compendium of Organic Synthetic Methods, Vol 11
690
CH2(CN), , umtmpine PhCHO
P h T C N mimwaves , 2 min CN Wanp.; Wei, B.; Hu, Y.; Liu, Z.; Kang, L. J. Chern. Res. (S), 200Z, 146
j & /
20% CsOH*H@, NMP
Koradin, C.; Rodriguez, A.;
I
1. 3
CN
,LDA,THF
C6H13
-90°C 4 -60°C 2.2M aq HCI Tetruhedron Lett., 2000, 41, 6201.
cat CpzVC12 CN
MqSiCl, Zn DMF,rt,2h
-
Ph
Ph
NC
NII2
Zhou, L.; Ilirao. T. Tetruhedron Lett., 2000, 41, 8517. CH2(CN), , NH40Ac, 6 min
.-
hasic A1203,microwaves
Balalale.~.; Namati, N. Synth. Commun., 2000, 30, 869.
PhCHO
NC 43)
Y.;Nishizaki, Y.; Sugi.
Y, Chern. Lett., 2000, 998.
NH2 72%
phvm 80%
CN
CHz(CN), , PhH ,20"C, 6 h (HDTMA+-[Si]-MCM-41
Kuhuta.
Ph
; *hp
(57
PhCHO
80%
Synlett, 2000, 1452.
c1
PhI IC*cN
-+ pL rt
Ph
cp-7-C6Hl CP Kasatkin, A.N.;
87%
CN
Section 377
Alkene - Allcene
-
SECTION 377:
ALKENE ALKENE 0
w
avo.
CHZSHCN, Pd(0Ac)Z t-amyl alcohol ,8372
y OEt OEt
O
69 1
K2C03,2 h
Y.;Arisha, A.H.I. J. Org. Chem., 2001, 66, 4921. ]LLCO2Me
H” , PhH (degassed) sealed tube, 240°C
,,&”
’b,,
H
‘e,
1 S e q BHT
Tf3so
*9: 34%
,,\”’
mso
Deak, H.L.; Stokes, S.S.; w n e r . M .L,J. Am. Chem. SOC.,200Z, 123, 51.52.
T f 2 0 ,DCM , Z64utidine
(10
:
I) 65%
Harmata.;Bohnert, G . ;Barnes, C.L. Tetruhedron Lett., 2001, 42, 149. 7% [CpRu(NCMqhYPF6-
-)=41(””
acetone/THF , H20 , - 2 0 T , 4 h
Trost. B.M; Rudd, M.T. J. Am. Chem. SOC.,2001, 123, 8862.
77%
0
Meo27
MeOZC
P(c12, dioxane 7 0 T , 20 h
MCndez, M.; Mufioz, M.P.; Nevado, C.; Ckdenas, D.J.; J . Am. C h m .
SOC.,2001, 123, 10.511.
Compendium of Organic Synthetic Methods, Vol 11
692
Section 377
10% CpRu( MeCNbPF6 15%CeC13.7 H 2 0 1.5MVK, DMF 60°C, 6 h
Trost. B.M,; Pinkerton, A.B.; Seidel, M. J. Am. Chem. SOC.,2001, 123, 12466
DMF , Ru catalyst, rt
oq
86%
Trost. B.M.; Pinkerton, A.B.; Toste, F.D.; Sperrle, M. J. Am. Chem. SOC.2001, 123, 12504. 0
PhCI I 0
~
wSi
Ph
TMSCl 2. H30' ,-78°C Lee, B.S.; Gil, J.M.; Qh. D.Y. Tetruherfmn Leu.,2001, 42, 2345. 10% CpRu(MeCmPF6 MeO2C
0.2M acetone, It
M
78%
e
0
2
c
Meo2C
Trost.;Toste, F.D.; Shen, H . J. Am. Chem. SOC.,2000, 122, 2379.
87%
a
Alkene - Alkene
Section 377
693
BocHN
BocHN
NIIBoc
10%C ~ R U ( N C M C )PF6~+
0
Trost. B.M.; Surivet, J.-P. Angew. Chent. Int. Ed., 200Z,40, 1468.
SiMe.,
Tf20 ,-60°C
2,6-lutidine CH,Cl,
-
+
(88 12) Suzuki, H.; Monda, A.; Kuroda, C, Tetruhedron LRtt., 2001, 42, 1915.
b.
CP2
“‘3Y
2 eqEtCuCl , THF Et , 1 h ‘
Xi, C.; Kotora, M.; Nakajima, K.;
*
81%
bEr
J. Org. Chenz.,2000, 65, 945.
1. Me(ZnI)z, 2% Pdz(dba)JCHCIs &33% 10%P(3,5(CF3)2C,H,h
2.
66%
111111
*
&Br
Matsubara.; Ukai, K.; Toda, N.; Utimoto, K.; Oshima, K. Synlett, 2000, 995.
\
Compendium of Organic Synthetic Methods, Vol 11
694
mSMeFz CuCl ,DMF ,air
Ph
*
rt,3h
Nishihara, Y.;Ikegashira, K.; Toriyama, F.; Mori. A.: ITiyama, T. Bull. Chem. SOC.Jpn., 2000, 73, 985.
10% Ni(PPh3)4, toluene
/co2Et
-15,C
+
-10°C ,30min
Section 377
om
Ph
98%
*
71%
COZEt Saito. S.; Hirayama, K.; Kabuto, C.; Yamam oto. Y, J. Am. Chem. SOC., 2000,122, 10776.
TBDM mD SnBr3
0
* M e 3S i d G H 1 '
1.1, ether, r t , 1 h
Me3Si&
OSnBr3 2' B u 3 S n \ / l i L , ~ d l l DMF ,PdQZ(MeCN)2 60"C, 6h 3. Si02 ; Parrain, J.-L.; Aharbri, M. Lunot, S.A.; nibonnet, J.; Tetruhedron Irtt., 2000, 41, 8893.
C0,Me10% CpRu(MeCN)3BF6
64%
t
0.1 M acetone, rt, 4 h
Trost.;Toste, F.D. J. Am.
Chem. SOC., 1999, 121, 9728.
1. BuLi, -78°C 2. CQI13Br M+Si
3. heat
*L c61T13
82~70%
B t = henzotxiazyl Katritzky, A.R.; Serdyuk, L.; Toader, D.; Wang, X. J. Org. Chem., 1999, 64, 1888.
P hCI I 0 ~
R
.
dsiMe3 , BuLi , ZnCl, .r
Ni(cod), Ph F Zaporowski, . ; L.F.; Rogers, M. J. Org. Chern., 1999, 64, 9307.
58%
Section 378
695
Oxide - Akyne
cr: 4-
10% Rh(PPh3hOTf bluene , 110°C 0.01M
MeO2C
Wender.;Dyckman, A.J. Org. Lett., Z999, 1, 2089.
SECTION 378:
96%
C02Me
OXIDES - ALKYNES
*fl-
S02Ph
:l;:u;:
~
Ar = 3,541nethylphenyl Me rurstner.; . . Mathes, C. Org. Lett., 2001, 3, 221.
Ph
Ph PhCPCfI , MeOH, NEt, 20% PdCl2,20% CUI
Ph B uTe
rt,8h
0
u; de Andrade, L.11.;Silveira, C.C.; Moro, A.V.;
73%
a;
Tetrahedron Lett., 2001, 42, 8563.
0
1 . NaH 2. NaH ,(EtO)zP(OfH
THF , CCh
EtO-P,
* EtO/
II
o \
L
Ph
62% (>95% ZE) Kahalka. G.W,; Yang, K.; Wang, Z. Synth. Conintun., 2001, 31, 511.
Section 380
Compendium of Organic Synthetic Methods, Vol 11
696
0
1. C a r ,THF,