Compendium of Organic Synthetic Methods

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Compendium of Organic Synthetic Methods, Volume 9. Michael B. Smith Copyright  2001 by John Wiley & Sons, Inc. ISBNs: 0-471-14579-3 (Hardback); 0-471-22822-2 (Electronic)

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods Volume 9 MICHAEL

B. SMITH

DEPARTMENT OF CHEMISTRY THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT

A Wiley-Interscience

Publication

JOHN WILEY & SONS, INC. New York

l

Chichester

l

Weinheim

l

Brisbane

l

Sinaar>ore

l

Toronto

Copyright  2001 by John Wiley and Sons, Inc., New York. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic or mechanical, including uploading, downloading, printing, decompiling, recording or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the Publisher. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold with the understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, the services of a competent professional person should be sought. ISBN 0-471-22822-2. This title is also available in print as ISBN 0-471-14579-3. For more information about Wiley products, visit our web site at www.Wiley.com.


CONTENTS PREFACE ABBREVIATIONS INDEX, MONOFUNCTIONAL COMPOUNDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION PREPARATION OF ALKYNES PREPARATION OF ACID DERIVATIVES PREPARATION OF ALCOHOLS PREPARATON OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENES AND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS 10 PREPARATION OF HALIDES AND SULFONATES 11 PREPARATION OF HYDRIDES 12 PREPARATION OF KETONES 13 PREPARATION OF NITRILES 14 PREPARATION OF ALKENES 15 PREPARATION OF OXIDES 16 PREPARATION OF DIFUNCTIONAL COMPOUNDS AUTHOR INDEX

vii ix ... XIII

xv

1 5 11 48 58 100 117 140 156 171 176 183 208 212 227 235 391

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 Iiterrature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Voume 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). 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 body of 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 9 contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1993, 1994 and 1995. The classification schemes used for volumes 6-8 have been continued. Difunctional compounds appear in Chapter 16. The experienced user of the Compendium will require no special insructions for the use of Volume 9. Author citations and the Author Index have been continued as in Volumes 6-8. 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 througout my writing career, I thank my wife Sarah and my son Steven who have shown unfailing patience and devotion during this work. I also thank Darla Henderson, the editor of this volume. Michael

B. Smith

Department of Chemistry University of Connecticut 55 N. Eagleville Road Storrs, Connecticut 06269-3060 Voice phone: (860)-486-2881 Fax: (860)-486-2981 Email: smith @Inucleus.chem.unconn.edu

vii

ABBREVIATIONS 0 AC

Acetyl

acac AIBN aq*

Acetylacetonate azo-bis-isobutyronitrile Aqueous

&

/

CH3

9-Borabicyclo[3.3.1]nonylboryl

B\9

9-BBN BER BINAP Bn Bz

9-Borabicyclo[3.3.1]nonane Borohydride exchange resin 2R,3S-2,2’-bis-(diphenylphosphino)-1,lr-binapthyl benzyl benzoyl

BOC

t-Butoxycarbonyl

0

&

Ot-Bu

Bu CAM CAN ccat.

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-2-01 1$Cyclooctadienyl 1,3,5cyclooctatrienyl Cyclopentadienyl Camphorsulfonic acid Cl&I33NMe3+Brcetyltrimethylammonium bromide

bPY WPY)

CY (+jH OC DABCO dba DBE DBN DBU DCC

11)

Cyclohexyl Temperature in Degrees Centigrade 1,4-Diazobicyclo[2.2.2]octane dibenzylidene acetone 1,2-Dibromoethane 1,8-Diazabicyclo[5.4.0]undec-7-ene 1,5-Diazabicyclo[4,3,O]non-5-ene 1,3-Dicyclohexylcarbodiimide

-CH2CH2CH2CH3 (NH)2Ce(NO3)6 0 &

OCH2Ph

+o

BrCH2CH2Br

c-C6H13-N=C=N-c-C6H13 ix

X

DCE

ABBREVIATIONS

% de DEA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DMA DME

1,2-Dichloroethane 2, 3-Dichloro-5,6-dicyano1,4-benzoquinone % Diasteromeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride 1,2-bis-(Diphenylphosphino)ethane 1,4-his-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dimethylacetamide Dimethoxyethane

DMF

N,N’-Dimethylformamide

DDQ

C1CH2CH2Cl

HN(CH2CH3)2 Et02C-N=NC02Et (Me2CHCH2)2AlH Ph2PCH2CH2PPh2 Ph2P(CH2)4PPh2

MeOCH2CH20Me 0 H

dmp dpm dPPb dPPe dPPf dPPP dvb e% ee EE Et EDA EDTA FMN fod FP FVP h hv 1,5-HD HMPA HMPT iPr LICA (LIPCA) LDA LHMDS LTMP MABR MAD mCPBA Me MEM Mes

K N(CH3)2

bis-[ 1,3-Di@-methoxyphenyl)1,3-propanedionato] dipivaloylmethanato 1,4-bis-(Diphenylphosphino)butane Ph2P(CH2)4PPh2 1,2-bis-(Diphenylphosphino)ethane Ph2PCH2CH2PPh2 bis-(Diphenylphosphino)ferrocene 1,3-bis-(Diphenylphosphino)propane Ph2P(CH2)3PPh2 Divinylbenzene Electrolysis % Enantiomeric excess EtO(Me)HCO1-Ethoxyethyl -CH2CH3 Ethyl H2NCH2CH2NH2 Ethylenediamine Ethylenediaminetetraacetic acid Flavin mononucleotide tris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-octanedionate Cyclopentadienyl-bis-carbonyl iron Flash Vacuum Pyrolysis hour (hours) Irradiation with light 1&Hexadienyl (Me3N)3P=O Hexamethylphosphoramide Hexamethylphosphorous triamide (Me3N)3P Isopropyl -CH(CH3)2 Lithium cyclohexylisopropylamide LiN(iPr)2 Lithium diisopropylamide LiN(SiMe3)2 Lithium hexamethyl disilazide Lithium 2,2,6,6-tetramethylpiperidide Methylaluminum bis-(4-bromo-2,6-di-tert-butylphenoxide) bis-(2,6-di-t-butyl-4-methylphenoxy)methyl aluminum meta-Chloroperoxybenzoic acid Methyl -CH3 MeOCH2CH20CH2P-Methoxyethoxymethyl 2,4,6-tri-Me-C6H2 Mesityl

ABBREVIATIONS

MeOCH2CH3SO2-

MOM MS MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) NMP Oxone

Methoxymethyl Methanesulfonyl Molecular Sieves (3Aor 483 Methylthiomethyl Nicotinamide adenine dinucleotide Sodium triphosphopyridine nucleotide Napthy CC1oH$ Norbornadiene N-Bromosuccinimide N-Chlorosuccinimide N-Iodosuccinimide Raney nickel N-Methyl-2-pyrrolidinone 2 KHS05.KHS04aK2S04

0P

Polymeric backbone

PCC PDC PEG

Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol

Ph

Phenyl

PhH PhMe Phth pit

Benzene Toluene Phthaloyl 2-Pyridinecarboxylate

Pip

Piperidine

PMP

4-methoxyphenyl

Pr

n-Propyl

-CH2CH2CH3

PY

Pyridine

N- \ / 3

quant. Red-Al sBu sBuLi Siamyl TADDOI TASF TBAF TBDMS TBHP (t-BuOOH) t-Bu TEBA TEMPO

Quantitative yield [(MeOCH2CH20)2AlH2]Na set-Butyl set-Butyllithium Diisoamyl a,a,a’,a’-tetraaryl-4,5-dimethoxy-1,3-dioxolane tris-(Diethylamino)sulfonium difluorotrimethyl Tetrabutylammonium fluoride t-Butyldimethylsilyl t-Butylhydroperoxide tert-B utyl Triethylbenzylammonium Tetramethylpiperdinyloxy free radical

J

CH3SCH2-

to\/ H-N

3

CH3CH2CH(CH3) CH3CH2CH(Li)CH3 (CH3)2CHCH(CH3)silicate n-Bu4N+F t-BuMe2Si Me3COOH -C(CH3)3 Bn(CH3)3N+

ABBREVIATIONS

xii

TFA TFAA Tf (OTf) THF THP TMEDA TMG TMS TMP TPAP To1 Tr TRIS Ts(Tos)

Trifluoroacetic acid Trifluoroacetic anhydride Triflate Tetrahydrofuran Tetrahydropyran Tetramethylethylenediamine 1,1,3,3-Tetramethylguanidine Trimethylsilyl 2,2,6,6-Tetramethylpiperidine tetra-n-Propylammonium perruthenate Tolyl Trityl Triisopropylphenylsulfonyl Tosyl = p-Toluenesulfonyl

N),,)

Sonication

xc

Chiral auxiliary

CF3COOH (CF3CO)20 -S02CF3(-OS02CF3)

Me2NCH2CH2NMe2 -Si(CH3)3

4-c#&H3 -CPh3 4-Mec6&

INDEX,

MONOFUNCTIONAL

COMPOUNDS

Sections--heavy type Pages--light type Blanks in the table correspond to sections for which no additional examples were found in the literature

Sect. Carboxylic Alcohols, Aldehydes

acids phenols

AmideS AIIli~S

Ketones

PREPARATION

Pg.

30A 45A 60A 90A 105A 180A

9 f: 115 137 206

OF ‘l

7

FROM

Alkynes

Catboxylic derivatives Alcohols,

1 1

acid phenols

31 11

Aldehydes Alkyls, methylenes, aryls Amid=

17 5

18 6

19 6

32 11

33 12

34 13

47 48

48 48

49 49

Ethers, epxoides Halides,

63

64

65

60

60

61

76 loo

77 100

106 140

107 140

121 156 137 171

166 183

167 184

Nitriles Alkenes Miscellaneous

78 101

80 102

52 51

98 129

99 129

113 146

114 148

109 144

111 145

123 156

124 158

128 159 140 172

184 208 199 217

1% 212

197 216

198 217

211 227

212 227

213 227

171 191

172 192

186 209 200 219

201 220

ml 178 173 193

12 3

14 3

15 3

25 7

27 8

29 8

30 9

44 39

45 41

40 29

41 30

55 52 70 65

129 160

159 179 174 193

188 209

71 70

203 220

204 221

217 228

218 228

219 228

59 54

70 55

87888990 112 113

113

113

103 132

104 132

105 133

118 153

72 71

101

130

131

102 131

116 150

117 151

115 149 130 161

131 161

132 161

145 173

146 173

147 174

160 179 175 195

162 181 176 1%

119 154 134 162 149 175

163 182

177 198

179 202

222 232

135 169 150 175

180 204 1% 211

207 223 221 232

120 154

165 182

192 210

20s 221 220 232

43 39 58 53

loo

1% 209

202 220

42 30 57 53

85 111

142 172 157 177

170 191

69 65

97 120

108 142

la3 208

54 52

83 110

96 119

169 189

53 51

82 108

94 118

168 186

39 26

81 102

93 117

138 171

24 7

38 26

68 64

153 176

(RH) Ketones

50 50

61

sulfonates

Hydrides

36 25

58

Amines Esters

23 7

10 2

223 233

209 223

210 225

234 233

225 233

*.. XIII

INDEX, Sections-heavy

DIFUNCTIONAL

COMPOUNDS

type

Pages-light type

Blanks in the table correspond to sections for which no additional examples wem found in the literature

305 337

316 242

326 252

335 283

343 288

307 238

318 243

328 261

337 284

345 290

309 239

320 244

310 239

L

311 239 378

xiv

322 244

352 309

358 325

363 340

359

364

330 267

347 293

354 312

340 330

365 344

331 274

348 296

355 315

361 334

366 350

332 276

341 284

349 296

356

362

367

380

381

382

383

384

385

368

386

INTRODUCTION Relationship between Volume 9 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 9 presents about 1200 examples of published reactions for the preparation of monofunctional compounds, updating the 10650 in Volumes l-8. Volume 9 contains about 800 examples of reactions which prepare of difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 9 adds almost 90 pertinent reviews in the various sections. Volume 9 contains approximately 1000 fewer entries than Volume 8 for an identical three-year period, primarily for difunctional compunds. Interestingly, there are about 500 fewer citations from the most cited journal (Tetrahedron Letters) than in the previous edition. Whether this represents a trend in the literature or an inadvertent selectivity on my part is unknown, but there has been a clear increase in biochemical and total synthesis papers which may account for this. Chapters l-l 4 continue as in Volumes l-8, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6 and 7. The sections on oxides as part of difunctional compounds, introduced in Volume 7, continues in Chapter 16 of Volumes 8 and 9 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 principle author is indicated by underlining (i.e., Kwon, T.W.; Smith, M. B.), as in Volumes 7 and 8. 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 ascending order of year cited (1993-1995), 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 PhCOOH, and PhCH=CHCH20H t-BuCOOH, PhCH20H PhCH=CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated xv

xvi

INTRODUCTION

ketones, aldehydes, esters, acids, and nitriles have been placed in Sections 740 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 - RCH2COOH (carboxylic acids from hydrides), RMe - RCOOH (carboxylic acids from alkyls), RPh - RCOOH (carboxylic acids from aryls). Note the distinction between R2CO - 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). The following examples illustrate the classfication of some potentially confusing cases: RCH=CHCOOH RCH=CH2 ArH ArH RCHO RCH=CHCHO RCHO R2CH2 RCH2COR RCH=CH2

- RCH=CH2 - RCH=CHCOOH - ArCOOH - ArOAc - RH - RCH=CH2 - RCH3 - R2C0 - R2CHCOR - RCH2CH3

RBr + HC-CH

-

RCH-CR

ROH + RCOOH

-

RCOOR

RCH=CHCHO

-

RCH2CH2CH0

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) Alkynes from halides; also al kynes from al kynes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Rduction)

How to Use the Book to Locate Examples of the Preparation of Protection Examples of the preparation of one funcof Monofunctional Compounds. tional group from another are found in the monofunctional index on p. x, 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 alkynes that form new alkynes; Section 16 gives reactions of alkynes that form carboxylic acids; and Section 31 gives reactions of alkynes 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 alkynes from alkynes; carboxylic acids from carboxylic acids; and

INTRODUCTION

xvii

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 frorm Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). Examples of the protection of alkynes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Section (designated with an A: 15A, 30A, etc.) with “protecting group: reactions 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 Compounds.

and Organization

of Reactions

Forming

Difunctional

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, nitrile, and alkene. Reactions that form difunctional compounds are classified into sections on the basis of two functional grups 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 1,4amino-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 (Ketone-Oxide). Conversion of an oxide to another functional grup is generally found in the “Miscellaneous” section of the sections concerning monofunctional com-

.. . XVIII

INTRODUCTION

pounds. 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: Difunctionaf Product RGC-C-CR RCH(OH)COOH RCH=CHOMe RCHF2 RCH(Br)CHzF RCH(OAc)CH20H RCH(OH)COzMe RCH=CHCH2C02Me RCH=CHOAc RCH(OMe)CH2SO2CH$H2OH RS02CH2CH20H

Section Et/e Alkyne-Alkyne Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Alkene Ester-Alkene Alcohol-Ether Alcohol-Oxide

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on pWxi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, ThiolEster) 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 carcompounds) or boxylic acids from halides (Section 25, monofunctional 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 compund. Such methods are difficult to categorize and may be found in either the monofunctional or 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

INTRODUCTION

xix

RCH(OAc)CH20Ac (ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH20H (alcohol-alcohol). Sources of Literature Citations. I thought it would be useful for a reader of this Compendium to see the distribution of citations used to this book (i.e., which journals have the most new synthetic methodology). As seen in the accompanying graph, Tetrahedron Letters and Journal of Organic Chemistry account for roughly 60% of all the citations in Volume 9. This book was not edited to favor one journal, category or type of article over another. Undoubtedly, my own personal preferences are part of the selection but I believe that this compilation is an accurate represention 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 “18 other journals” includes: Accts. Chem. Res.; Acta Chem. Stand.; Angew. Chem. Int. Ed. Engl.; Bull. Chim. Sot. Be/g.; Bull. Chim. Sot. Fr.; Can. J. Chem.; Chem. Ber.; Gazz. Chim. Ital.; Heterocycles; J. Chem. Sot.; J. Het. Chem.; J. Indian Chem. Sot; Liebigs Ann. Chem.; Org. Prep. Proceed Int.; Reel. Tram. Chim., Pays-Bas; and Tetrahedron Asymmetry. In addition, nine more journals were examined but no references were recorded.

18 other journals

KS Perkin I

Tetrahedron

Bull Chem Sot Jpn

Synthesis

JACS

Synth Commun

JCS, Chem Comm

Chem Lett

SynLett

J. Org. Chem.

Tetr. Lett.

Citations

xx INTRODUCTION

Compendium of Organic Synthetic Methods


CHAPTER

1

PREPARATION

SECTION

OF ALKYNES

1: ALKYNES

FROM

ALKYNES

Me2CHCH21,

THF

--------SiMePhz

t ;SiMePh,

SmIzSm

80% Murakami.

M,; Hayashi, M.; Ito. YJynlett,

1994,

179 Ph

(CH2)40AC

Ph

Ph , toluene

5% MO(C0)6 , llO°C , 2o”c 4-chlorophenol

AcO(H2C)4

Kaneta, N.; Hikichi,

E

AcO(H2C)4

K.; Asaka, S.; Uemura, M.; Mori, M. Chem. L&t., 1995,

80% 1055

REVIEW: “Palladium And/Or Copper-Mediated Cross-Coupling Reactions Between 1-Alkynes And Vinyl, Aryl, 1-Alkynyl, 1,2Propadienyl, Propargyl And Allylic Halides Or Related Compounds. A Review,” Rossi. R,; Carpita, A.; Bellina, F. Org. Prep. Proceed. Znt., 1995, 27, 129

SECTION

2: ALKYNES

FROM

A4CID DERIVATIVES

NO ADDITIONAL

SECTION

3: ALKYNES

FROM

ALCOHOLS

NO ADDITIONAL

SECTION

4: ALKYNES

FROM

EXAMPLES

AND THIOLS

EXAMPLES

ALDEHYDES

NO ADDITIONAL

EXAMPLES

Compendium

SECTION

5:

of Organic Synthetic Methods, Vol9

ALKYNES FROM AND ARYLS

ALKYLS,

NO ADDITIONAL

SECTION

6:

ALKYNES

FROM

7:

ALKYNES

AMIDES

FROM

EXAMPLES

AMINES

NO ADDITIONAL

SECTION

8:

ALKYNES

FROM

EXAMPLES

ESTERS

NO ADDITIONAL

SECTION

9:

ALKYNES FROM THIOETHERS

EXAMPLES

ETHERS,

NO ADDITIONAL

SECTION

10:

ALKYNES

METHYLENES

EXAMPLES

NO ADDITIONAL

SECTION

FROM

EPOXIDES

HALIDES

AND SULFONATES

HO.++K2C03

N.D.P, Synlett, 1995,

AND

EXAMPLES

-NO2

Pd/C , PPh3, CuI , DME

Bleicher, L.; Cosfwd.

Section 10

98% 111 5

Bu &@s. R.W.; Gabel, C.J.; Ji, J. Tetrahedron

Lett., 1994, 35, 6993

Section 15

SECTION

Alkynes from Misc.

11:

ALKYNES

FROM

HYDRIDES

For examples of the reaction RC=CH + R&C-C=CR1, (Alkyne-Alkyne). NO ADDITIONAL

SECTION

12:

ALKYNES

FROM

0

2

Ph I\

Taniguchi,

KETONES

Y.; Takai, K.; Fujiwara,

TMSC(Li)Nz,

THF

-78OC + reflux Me Miwa, K.; Aoyama. T.: Shioiri, T, Synlett, 1994,

13:

ALKYNES

FROM

14:

Ph

=

Ph

ALKYNES

FROM

67% Y. Chem. Lett., 199% 1165

*

P-Me

58%

107

NITRILES

NO ADDITIONAL

SECTION

*

-1OOC ,20 min

SiMe3

Y.; Fujii, N.; Makioka,

SECTION

EXAMPLF;

Yb,THF,HMPA

0

see section 300

EXAMPLES

ALKENES OSiPhzt-Bu

NaHMDS , THF -100°C Grandjean, D.; Pale, P.; Chuche, J. Tetrahedron

SECTION

15:

ALKYNES

FROM

V

98%

L&t., 1994, 35, 3529

MISCELLANEOUS

COMPOUNDS

FVP (750°C) w t-Bu

Aitken. From A&ken. 1994,

=t-Bu

82% R,A,; Atherton, J.I. J. Chem. Sot., Per-kin Trans. l., 1994, 128 1 arylC0 derivatives: R.A.; Horsburgh, C.E.R.; McCreadie, J.G.; Seth, S. J. Chem. Sot., Perkin Trans. l., 1727

4

SECTION

Compendium

15A:

of Organic Synthetic Methods, Vo19

PROTECTION

OF ALKYNES

NO ADDITIONAL

EXAMPLB

Section 15A


Section 17

Acids from Acids

CHAPTER

2

PREPARATION

SECTION

16:

SECTION

OF

ACID

ACID DERIVATIVES

ACID

17:

DERIVATIVES

FROM

NO ADDITIONAL

EXAMPLES

DERIVATIVES

FROM

ALKYNES

ACID

DERIVATIVES

C02H HO

HaG,, @b, A BuLi, THF-HMPA

A I

v

*

OTs

+

6

Jv

d

OMe Me0

Me0

.

Kusumoto.T.;

1) 82% (10 Ichikawa, S.; Asaka, K.; Sato, K.; Hiyama, T. Tekhedron Lett., 1995,

36,

0 C02H

KF , microwave,

4 min 0

OAc

C02H
95%ee]

Mikami. K,; Yajima, T.; Terada,M.; Uchimaru, T. Tetrahedron Mt., 1993, 34, 7591 mSnBu3

, MS4A, CH2C12 t 20% (binol)TiClz , rt , 2d

PhCHO

96% (82% ee , S) Costa, A.L.; Piazza, M.G.; Tanliavini, E,; Trombini, C.; 1[Jmani-Ronchi. A, J. Am. Chem. Sot., 1993, 115, 7001 1.

Ti(OiPr)dl,l’-bi-2-naphthol , MS4A CH2C12,reflux

PhCHO

-78OC,10 min 2. m

OH Phk

SnBu3 , -20°C, 70h

88% (95% ee, R) J(eck. G&; Tarbet, K.H.; Geraci, L.S. J. Am. Chem. Sot., 1993, I15, 8467 1. Et$Zn ,25OC, 10% Lie\\\\\ PhCHO 2.2N HCl 80% ee Mehler, T.; Martens.;

Wallbaum, S. Synth. Commun., 1993, 23, 269 1

1. ZnEt2 , 10%

CP

PhCHO

N H

11”1CPh20H

OH

2.2N HCl , -2OOC 100%ee Wallbaum, S.; m. J, Tetrahedron Asymmetry, 1993, 4, 637 With a chiral oxazoline additive, 60% ee J.m Tetrahedron Asymmetry, 1993, 4, 649 Allen, J.V.; Frost, C.G.; W-s.

16

Compendiumof Organic Synthetic Methods, Vol9

Section34B

1. BuLi 2. PhCHO

h

CPhzOH

OH

N Me

3. znEt2

4.2N HCl

Behnen, W.; Mehler, T.; Martens. TI Tetrahedron Asymmetry, 1993,4, 1413

OH

Et2Zn , toluene , hexane

PhCHO

98% ee , S

-

A 95% (85% ee, R)

Et

de Vries, E.F.J.; mee. 1987

Fit

J,; Kruse, C.G.; van der Gen, A. Tetrahedron Asymmetry, 1993, 4, OH

ZnEt2,5% iPr2NH

PhCHO

y i

5%

*

PhL

Ph-

quant. (46% ee , R) ShengJian, L.; Yaozhonrr. J,; Aiqiao, M.; Guishu, Y. J. Chem. Sot., Perkin Trans. I., 1993, 885 Et2Zn . PhMe , rt PhCHO

90% (96% ee , R) ao.

Rx;

Kim, N. Tetrahedron Lett., 1994, 35, 4115 CHo I

Me2Zn , PhMe , O°C, NHTf

Ti(Ot-Bu)4,8% TTPWI

I

a

NHTf

with Ti(OiPr)d - 80% yield, 0% ee Nowotng, S.; Vettel, S.; Mel, P, Tetrahedron Lett., 1994, 35, 4539

17

Alcohols from Amides

Section 36

Bu$n PhCHO , (R)-Binol +

0.5 Ti(OiPr), , -2O”d /

..

(14

1) 48%

>99% ee Keck. G.E,; Krishnamurthy, D.; Chen, X. Tetrahedron Lett., 1994, 35, 8323 PhCHO

OH

ZnEtz , hexaneftoluene, 10% chiral ligand 20°C, 28h

72% (80% ee) Perez-Encabo,A. Tetrahedron Asymmetry, 1994, 5,

And&, KM.; Martinez, M.A.; Pedro-; 67

ZnEt;! ,5% chiral ligand PhCHO

16h 70% (68% ee , R)

Ishizaki, M.; Fujita, K.; Shimamoto,M.; -0.

0, Tetrahedron Asymmetry, 1994, 5, 411

H

Et$Zn

PhCHO

*

Me%4 * N 3

P h\‘\\\c

Ph-L

SH

94% (100% ee)

Kanrz, J,; Lee, J.W.; Kim, J.I. J. Chem. Sot. Chem. Commun., 1994, 2009

CHO

P ’

0

Ph

Watanabe,M.; Soai.

\

OH

Et$n ,18h

0

Ph J. Chem. Sot., Perkin Trans. I., 1994, 3125

quant. (93% ee)

18


Et$Zn ,22OC

H

PhCHO 10% Stingl, K.; w.

~111 CH (Mes)OLi

00

Section34B

) *

PhL 70-90% (86% ee , S)

N Bn

J, Liebigs Ann. Chem., 1994,49 1 Et$n , chiral ferrocenecatalyst

PhCHO

85% (55% ee , R)

toluene mawa.

S,; Tsudzuki, IS. Tetrahedron Asymmetry, 1995, 6, 1039

PhCHO CH2C12, -78OC

Phw 93% (79% ee)

I(obavashl.. S,; Nishio, K. Tetrahedron L&t., 1995, 36, 6729 Bu3Sn-

, CH2C12,MS * c7H15L 58% (87% ee) 20% Zr-BINOL derivative Bedeschi,P.; Casolari, S.; Costa,A.L.; Tagliavini, E,; Umani-Ronchi, A. Tetrahedron Lett., 1995, 36, 7897 C7H&HO

1. chiral Ti complex , ether Ph/

CHO *

2TFA,THF

pi0

OTMS 97% (80% ee) Singer, R.A.; &reira.

E.M, J. Am. Chem. Sot., 1995, 117, 12360

NON-ASYMMETRIC Sn(CH$H=CH& Ph-

ALKYLATIONS

, D-arabinose, rt

CHO 5% Sc(OTf), , aq. MeCN

Hachiya, I.; Kobayashi, S. J. Org. Chem., 1993, 58, 6958

*

PhL

98%

Section 36


/m

Ph

19

PhCHO , Et$n , THF cat. Pd(PPh& , rt ,3h

H I

0

-

PJJ

88% Yasui, K.; Goto, Y.; Yajima, T.; Taniseki, Y.; Fugami, K.; Tanaka, A.; Tamaru. Y, Tetrahedron Lett., 1993, 34, 7619 diethyl ether, -5OOC PhCHO

98% t-Bu-

Et

(99 syn;anti) Wissing, E.; Havennith, R.W.A.; Boersma, J.; Smeets, W.J.J.; Spek, A.L.; van Koten, G,J. Org. Chem., 1993, 58, 4228 BuCHO + t-BuCHgHO

t

Ph

Bu OH

PhTi(OiP& , -4OOC 2 MAPH , PhLi , -78OC

Ph

t-BuHg +

OH 1) 60% 10.8) 60%

.. ..

(3 3 (1’

MAPH = ArOAr, Ar = 2,5diphenylphenyl Maruoka, K.; Saito, S.; Conception, A.B.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 1183 , THF/aq. HCl

C7H fi---CHO

20°C, lh

*

C7Hl5L

>99% Yanagisawa, A.; Inoue, H.; Morodome, M.; Yamamoto. H, J. Am. Chem. Sot., 1993, 115, 10356 e

SnBu3

, CH2C12, 25OC

PhCHO

83%

5% Ir(CO)(PPh&C104, 30h Nuss. J.M,; Rennels, R.A. Chem. Lett., 1993, 197 1. e

I

, SnC12.2 Hz0 *

PhCHO NaI,DMF

,hL

2,30%NH4F,H20 89% Imai, T,; Nishida, S. Synthesis, 1993, 395

20

Compendiumof Organic Synthetic Methods, Vo19

Section34B

1. Bu$nSiMe3, THF, rt 3h,Bu@CN

PhBCHO

2. H30+

SnBu3

Bhatt, R.K.; Ye, J.; Falck. J.R. Tetrahedron Lett., 1994, 35, 4081

m

PhCHO

SnBu3

5% Yb(OTf)3 85% Aspinall, H.C.; Browning, A.F.; Beeves N,; Ravenscroft,P. Tetrahedron Lett., 1994, 35,4639 mBr

,DMF,rrt *

ph/\/CHo GeI2 , lh

Phi 85%

Hashimoto, Y.; Kagoshima, H.; -0.

K, Tetrahedron Lett., 1994, 35,4805

OTIPS TIPS0

Ih40#‘,,, OTIPS /

1 C@ &HO , Me2AlCl , hexane -78OC,17h

SMe chirality

transfer

ene reaction

Masaya, K.; Tanino, K.; Kuwajima. I, Tetrahedron Lett., 1994, 35, 7965

BuGn-noMe :.I::b’” *-780zpJOMe

OMe

90% (70:30 de) Colombo. L,; DiGiacomo, M.; Brusotti, G.; Delougu, G. Tetrahedron Lett., 1994, 35, 2063 H

1. Li (powder) , naphthalene PhS02Et 2. Li (powder) , naphthalene * 3. PhCHO Guijarro, D.; m.

b& Tetrahedron Lett., 1994, 35, 2965

E -(I

61% Ph

Section 36


21

*3

SiMQ

sink3

l.Ga,KI,LiCl PhCHO , TI-IF , reflux w 2. H30+ H 4 Br

+ H

,8‘

x

Ph

Ph ..

(91 Han, Y.; Huansz. Y.-Z, Tetrahedron Lett., 1994, 35,9433

C,H7-

SnBug

-

cd413cHo

9) 95%

+

H

HO

w7

BuSnC13, CHCl3 , O°C

..

(98 Mipki.

2) 86%

H,; Yamamura, K. Chem. Lett., 1994, 897 10.5 CuCl , THF ) It

1. mBr

t

PhCHO 1.5 SnClp2 Hz0 , Id 2.30% aq. NI-IP

PhL 98%

T.Y; Nishida, S. J. Chem. Sot. Chem. Commun., 1994, 273

m

Ph EtCHO , Zn , aq. NH&I, Ph-Cl

Et

OH 98% (73:27) Rairama, R.; Ahonen, M. J. Chem. Sot. Chem. Commun., 1994, 1217

WR.; l

THF *

. .

cat. Pd(PPh& , PhCHO wso2ph

Et+,

THF , reflux

Ph 86%

Clayden, J.; lulia.M,

J. Chem. Sot. Chem. Commun., 1994, 1905

22


mso2ph

l*

Section 34B

pd(pph3)4

2.2 Et2Zn , CgHlgCHO THF , reflux Clayden. JJ Julia, M. J. Chem. Sot. Chem. Commun., 1994,226l Ph PhCHzSiMe3, hv , MeCN

OSiMe3

Mg(C104)2, 6.5h

Fukuzumi. S,; Okamoto, T.; Otera. J, J. Am. Chem. Sot., 1994, 116, 5503 Cl 2: PhCHO ,THF , -78OC ’ Ba* c7Hyph+ C7H15

HO47Hfi

d

Ph ..

3) 80% (>99:1 E.-z) Yanagisawa, A.; Habaue, S.; Yasue, K.; mamoto. K J. Am. Chem. Sot., 1994, 116, 6130

(97

CHO

QH = MSnBu3

> InC13, acetone, Sh , -78OC+ rt (98:2 anti:syn)

Mar&B.

J.k; Hinkle, K.W. J. Org. Chem., 1995, 60, 1920 1. PhCHO , DMF , O°C

mSiQ3

2. H20 Kobavashi. S,; Nishio, K. J. Org. Chem., 1995, 60, 6620

Ph

Section 36


C@$rCpCi ,20% ZnBr2 * THF ,3h, 25OC

PhCHO Zheng, B.; Bebnik.

23

Hz0

88%

J. Org. Chem., 1995, 60, 3278 In, H20,30 min

PhCHO

Br&

-

::OH Ph

Br

75%

I& C-J, Tetrahedron Lett., 1995, 36, 517

Me 1. Ti(OiPr)4 , iPrMgC1

4

+

OH

HO

i Ph . 84) 81% (16 Harada,K.; Urabe, H.; Sate. FcTetrahedron Lett., 1995, 36, i203 Nakagawa,T.; Kasatkin, A.; Sate. F, Tetrahedron Lett., 1995, 36, 3207

~cHooo

1. TMSOTf, CH& MqS , -78°C

--

2. Bu$nCH2CH=CH2 -40°C 3. TBAF

d3 (>99

m.

:

OH

’ 91% MPMO Kanq. S.-K,; Park, D.-C.; Park, C.-H.; Jang, S.-B. Synth. Commun., 1995, 25, 1359


Section 36

BrN

PhCHO

25

, Sn , Me$iCl 89%

Bu&Br , MeOH, rt ,4h Zhou, J.-Y.; Yao, X.-B.; Chen, Z.-G.; Wu. S.-H,Synth. Commun., 1995, 25, 3081

PhCHO

aSnBu3 ,THF,lt,4d * PhL

90%

pta2(pph3)2

Nakamura, H.; Asao, N.; mote.

w

Y, .I. Chem. Sot. Chem. Commun., 1995, 1273

13CHO

CH2C12-H20 (9.1 .. . H20, Bu$JBr (1 asuama. Y,; Kishida, M.; Kurusu, Y. J. Chem. Sot. Chem. Cohun.,

9) 48% 99) 48%

1995, 1405

REVIEW: “Synthetic Organoindium Chemistry: What Makes Indium So Appealing,” Cintas. P, Synlett, 1995, 1087

ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLS

SECTION 35:

No examplesof the reaction RR1 + ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactionsof the type RH + ROH (R = alkyl or aryl) seeSection 41 (Alcohols and Phenolsfrom Hydrides). NO ADDITIONAL EXAMPLES

SECTION 36: ALCOHOLS AND THIOLS FROM AMIDES 0 C6h3

LiBH3P-Pyr , THF, 25OC LA

*

N Pyr = pyrrolidino \3

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sinearam. B, Tetrahedron Lett., 1993, 34, 1091

(-13\/\OH

71%

26


Section 39

SECTION 37: ALCOHOLS AND THIOLS FROM AMINES NO ADDITIONAL EXAMPLES

SECTION 38: ALCOHOLS AND THIOLS FROM ESTERS Pi,

180°C, 15h

e H+Bu 68% OBu Vega, F.R.; Clement, J.-C.; des Abbayes,H. Tetrahedron Lett., 1993, 34, 8117 Mg , MeOH, rt ,2.5h Me0 Y.-C,; Lebeau,E.; Walker, C. Tetrahedron Lett., 1994, 35, 6207

98%

1. PMHS , Ti(OiPr)J , THF Ph-C&Me

t

2. NaOH

PhCH20H

86$

PMHS = polymethylhydrosiloxane Breedon, S.W.; bwrence. N.J, Synlett, 1994, 833 1.2.5 eq. PHMS ,25% Ti(OiPr)d 65OC, Id CgHlg-COzEt t 2. aq. NaOH , THF Reding, M.T.; Buchwald. S.L,J. Org. Chem., 1995, 60, 7884 C7HfiCH2SAc

OH C9H19

93%

BER , Pd(OAc)z , MeOH, reflux w C7HfiCH2SI-I

BER = borohydride exchangeresin Choi, J.; Yoon. N.M,Synth. Commun., 1995, 25, 2655

SECTION 39:

/

98%

ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS Bu,CuCNLi2,

THF OH

products are converted to alkenes via Swem oxidation and elimination

(95

Chauret, DC.; Bong, J.hl, Tetrahedron Lett., 1993, 34, 3695

+ :

Bu 5) 8040%

Section 39

Alcohols from Ethers

27

OH

OH

YJ

v

Al(Hg) , 10% aq. NaHC03

yield is 23% without ultrasound

also used Zn rather than Al(Hg)

ando Moreno. M.J.S SacMelo, M.L.; CamposNeves, A.S. hedron Lett., 1993:‘34, 353 Salvador, J.A.R.; S&eMelo. M.L,; CamposNeves, A.S. Tetrahedron Mt., 1993, 34, 361 l

Phi , Pd(PPh&$

, Zn , ZnCl2

Ph

THF,60°C,4h,NEt3 Duan, J.-P.; Chew. C-H, Tetrahedron Lett., 1993, 34,4019 1. LiI , MeCN , Amberlyst 15 rt, 30min MOTS

***+o = 3

= = &H

2. Bu$nH , AIBN , 80°C toluene ,2h

MOT,

Federici, C.; &i&i. G,; Rossi, L.; B Lett., 1994, 35, 797

99~88%

C,; Chiummiento, L.; Funicello, M. Tetrahedron

H2, Pd-C ,16h

t

P-OH HO

86%

Me

Bach, T, Tetrahedron Lett., 1994, 35, 1855

l\ aI

OH ’ 10% Pd(OAc)z

5 eq. NaO$H ,2 eq. BufiCl 3 eq. iPr2NEt , 80°C, Id N,N-dimethylacetamide Larock. RC,; Ding, S. J. Org. Chem., 1993, 58, 804

I (69:31 E.2)

70%

28


zH *aa

Section 39

Mg , MeOH

,,,\I@ / BnO

7-L

C02Me

H

98%

p;als. CA; Lee, E.; Lee, G.H. J. Org. Chem., 1993, 58, 1523

Pd/C , HCO2NH4, EtOH

0 w-h7

OH /

Al

23OC, 2d

W-h

Dragovich. P.S,; Prins, T.J.; Zhou, R. J. Org. Chem., 1995, 60, 4922

A

81%

98% Beugelmans, R.; Bourdet, S.; Bigot, A.; Zhu. L Tetrahedron Lett., I994, 35, 4349

)

Te9LiBT3,n

)

I

TsO Kumar, A.; m.

4

D.C: Tetrahedron Let?., 1994, 35, 5583 L-Selectride , THF ,67OC, 12h

Wheless, K. Tetrahedron Let?., 1994, 35, 8727

1. TMSN3 , W(Nt-Bu)2(NHIt-Bu)2 ,5d w

Ph

2. H+

OH

95%

[ with Cr(Nt-Bu)2C12;12h - 95% ] Leunn. W.-H\; Chow, E.K.F.; Wu, M.-C.; Kum, P.W.Y.; Yeunrr. L.-L, Tetrahedron Let?., 1995, 36, 107

29

Alcohols Tom Halides

Section 40

Ph

5% SmI2(THF)z, CH2C12

NEt2

Et2NH,rt,18h

(100

OH

+

..

0)

63%

regioselectivity of addition reversedwith Me&N3 to form azide-OTMS Van de Weghe, P.; collin. Tetrahedron Lett., 1995, 36, 1649

0

TMSN3, Ph&bOH, PhH reflux ,2h

67% 19% .. Funwara. M.; Tanaka,M.; Baba, A.; Ando, H.; Souma,Y. Tetrahedron Lett., 1995, 36, 4849 l.e-,Ni(II),Mganode,DMF,rt mOPh

*

PhOH

2. Hz0 99%

Olivero, S.; Dufiach. E, J. Chem. Sot. Chem. Commun., 1995,2497 Additional examplesof ethercleavagesmay be found in Section45A (Protection of Alcohols and Thiols).

SECTION 40:

ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES

02N-(-)-Br :::v::02N-(-)

\a

Bieniarz. C,; Cornwall, M.J. Tetrahedron Lett., 1993, 34, 939

I

a.

.

/

Br

siMe3

1. Li dispersion, ether reflux 2. PhCHO , -1OOC lh

also works with ketones M; Hatano,K.; Kimura, M.; Watanabe,T.; Oriyama, T.; Koga, G. Tetrahedron Lett.,

1994, 35, 579

30


Section42

1. Me3ZnLi , THF , -78OC

Ph-I

2. Me3Al, CHg12, O°C, lh

Ph 55%

Kondo, Y.; Takazawa,N.; Yamazaki, C.; Sakamoto.,J. org. chem., 1994, 59,4717

PhCHO -

PhCHCl2 2. NaB0~4 H@ ,2h

m

H

1. Bug , t-BuLi , -78OC

PC15

-

PhJL

G.W.; Lin, N.-S.; Yu, S. Tetrahedron Let?., 1995, 36;8545

Bu 64%

NHBn

NHBn

0 Yang, R.-Y.; Dai. I..-& Synth. Commun., 1994, 24, 2229

G Br

1. HC02NHEt3

CO2H 2.H20

80% J,; Renyer, M.L.; Veerapanane,H. Synth. Commun., 1995, 25, 3875

Mer.

SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES

0\ /

1. e- , CF$02H, CH2C12,NEt3

*

2.H20

(t\ /

Fujimoto, K.; Maekawa, H.; Tokuda, Y.; Matsubara,Y.; Mizuno, T.; Nishiguchi.

OH 73% SYnlett,

1995,661

SECTION 42: ALCOHOLS AND THIOLS FROM KETONES The following reaction typesare included in this section: A. Reductionsof Ketonesto Alcohols B. Alkylations of Ketones,forming Alcohols Coupling of ketonesto give diols is found in Section 323 (Alcohol + Alcohol).

Section42A

Reductionof Ketones

31

SECTION 42A: REDUCTION OF KETONES TO ALCOHOLS ASYMMETRIC

REDUCTION OH = Z I

BH3, THF , 80°C w

> 90% (92% e-e,R)

P ii

Quallich. GJ,; Woodall, T.M. Tetrahedron Lett., 1993, 34,4145

Me

85% (76%ee,R)

2.1N HC1 P Me Balm. (3,; Elder, M. Tetrahedron Lett., 1993, 34, 6041 G. candidium

CQzEt N

C02Et cyclopentanol H20, 70h

(7193syn:anti)

Me QH E _=

immobilized G. candidium hexane ,3h cyclopentanol

-/I/

(955 syn:anti)

G. candidium = Geotrichum candidum

Nakmura. KJ Takano, S.; Ohno, A. Tetrahedron Lett., 1993, 34, 6087 0.6 BHpSMe2 , THF rt,clh Me

M

10%

PA

R

H *

Y H

OH = =

+

Phl

P&Me

Me

P ’ ‘Ph

82% (27%ee,S)

Bums, B.;,Studley, J.R.; Wills. M, Tetrahedron Lett., 1993, 34, 7105

1.ld4j~; P

P

Me$iCl Me

2.2N HCl

H *

C02Et = = = = I

PhL

Me

92% (84% ee, R)

&-&IL C,; Seger,A.; Felder, M. Tetrahedron Lett., 1993, 34, 8079

32

Compendium of Organic Synthetic Methods, Vo19

Section 42A

2. SmI3, THF , ICHgH21 3. quench quant. (97% ee , R) Evans. D.pL; Nelson, S.G.; Gag&, M.R.; Muci, A.R. J. Am. Chem. Sue., 1993, 115, 9800 OH

1. P-TADDOL complex , Ph2SiH2 , PhH

50% (29.5:70.5 R.-S)

r~mw112 2. TsOH , MeOH

-APh

TADDOL = a,a,a’,&tetraaryl-4,5-dimethoxy-1,3-dioxolane Jakaki, J.-i.; Schweizer, W.B.; Seebach. D, Helv. Chim. Acta, 1993, 76, 2654 Bakers yeast (cell free extract) OAc

Ishihara, K.; Sakai, T.; Tsuboi, S.; IJtaka, 0

OAc

NaDPH ,8h

62% (>99% ee, S) Tetrahedron Let?., 1994, 35,4569

[ (COD)Rh(DiPFc) 1’ OTf H

Ph A

60 psi H2 ,25OC ,4h

L Ph

OH

DiPFc = 1, l’-bis-(diisopropylphosphino)ferrocene quant. Burk. MJ,; Harper, T.G.P.; Lee, J.R.; KaIberg, C. Tetrahedron Let?., 1994, 35, 4963

dcl

loIH3@g;;

dcy%@l.7%e,sJ

Hong, Y.; &D. Y.; Nie, X.; Zepp, C.M. Tetrahedron Let?., 1994, 35, 6631 Ph

1. Ph$iH2 ,5% Rh-diferrocenylTHF , o”c dichalcoginide

Ph *

67% (50% ee , R) 2.0.5M HCI/MeOH 0 OH Nishibayashi, Y.; Singh, J.D.; Segawa, IS.; Kukuzawa, S.i.; Uemura, S, J. Chem. Sot. Chem. Commun., 1994,1375

Section 42A

Reduction of Ketones

Bakers yeast sugar

OH

SH

C02Et

+

CO2Et

C02Et

.. (77 55% ee Tetrahedron Asymmetry, 1994, 5, 403

Nielsen, J.K.; Madsen.

Me

33

/L

23

immobilized Geotrichum candidurn

i)H = =

w hexane 2-hexanol

Ph

MeA

Ph

73% (>99% ee , S) Nakamura. K,; Inoue, Y.; Ohno, A. Tetrahedron Lett., 1995, 36, 265 OH

0

OH Ph

OH

(-)-B -chlorodiisopinocampheylborane -15OC + OOC, THF, pyridine

Ph

99% (96.4% ee) . Shteh. W.-C,; Cantrell Jr., W.R.; Carlson, J.A. Tetrahedron Lett., 1995, 36, 3797 Hz, (S-BINAP)zRuBrz COzMe

* MeOH, rt ,48h

OH == =

C02Me

80% (97% ee)

Genet.; Ratovelomanana-Vidal, V.; Ctio de Andrade, M.C.; Pfister, X.; Guerreiro, P.; Lenoir, J.Y. Tetrahedron Lett., 1995, 36, 4801

iL

H2 , iPrOH , chiral bis-phosphine

H

>99% (87% ee, R) * PhL chiral bis-amine Ph Ohkuma, T.; Ooka, H.; Hashiguchi, S.; Ikariya, T.; Novori. R,, J. Am. Chem. Sot., 1995, 117, 2675

4

Ph

[RuC12(mesitylene)]2, KOH , 15h TolO$HN+

/-f

Ph

N

NH2

Ph

Hashiguchi, S .; Fujii, A.; Takehara, J.; Ikariya, T.; &yori. 7562

OH PhA 95% (97% ee, S) & J. Am. Chem. Sot., 1995, I1 7,

34

Section 42A

Compendium of Organic Synthetic Methods, VoI 9

1. Ph2SiH2 , THF , 1% RhCl(NBD)zL chiral ferrocenyl phosphine ligand

0

OH 90% (87% ee , S)

PhA 2. H30+ * PhA . Havashl. T,; Hayashi, C.; Uozumi, Y. Tetrahedron Asymmetry, 1995,6, 2503 1.0.1 chiraI diol , hexane , -3OC , catecholborane 2. H30+ quant. (82% ee) Giffels, G.; Dreisbach, C.; Kragl, U.; Weigerding, M.; WaIdmann, H.; Wa~&ey. C1,Angew. Chem. Int. Ed. Engl., 1995, 34, 2005

NaBH4, EtOH Co (P-oxoaldiminato) complex

99% (73% ee , S) Nagata, T.; Yorozu, K.; Yamada, T.; Mukaiyama. T,Angew. Chem. Int. Ed. En& 1995, 34, 2145

NON-ASYMMETRIC

o= 0

REDUCTION

1. CdCl$Mg (powder) THF,15min

OH

92%

2, H20

Bordoloi. M, Tetrahedron Lett., 1993, 34, 1681

t-Bb

. olrm

(-)

o

LiAIH(zt2cMe3)3

~

t-Bu

with LiAlH(OCMe3)3 - 90: 10 trans:cis Cr.; Deberly, A.; Toneva, R. Synlett, 1993, 585

(-)

OH

5:95 trans:cis

Cu(I1) exchanged cationic resin ‘.,u-(-=’

NaBH4, EtOH, O°C

*

t-Bu-(-)-oH 98%

Sarkar. A,; Rao, B.R.; Ram, B. Synth. Commun., 1993, 23, 291

35

Reduction of Ketones

Section 42A

& :;:I;;

&

Fuller, J.C.; Staangeland, E.L.; Goralski, C.T.; Sinearam.

o=

Tetrahedron Lett., 1993, 34, 257

iPrOH , SiO2-Zr catalyst

0

Inada.;

92%

OH

reflux

87%

Shibagaki, M.; Nakanishi, Y.; Matsushita, H. Chem. Lett., 1993, 1795

0

OMe TiC14, MeflBH4 t

Ph

CH2C12 , -78°C

Ki other reducing agents also used Sarko, CR.; Guch, I.C.; Dime.

t-Bu

do

(99 M, J. Org. Chem., 1994, 59, 705

Liz;;;;H7)2

t ,:

1)

:

93%

&OH

99% Harrison, J.; Fuller, J.C.; Goralski, CT.; Singaram. B, Tetrahedron Lett., 1994, 35, 5201 OH

0 1. Cp2TiC12/NaBHq, 5 min 2.1 N NaOH % Barden, M.C.; Schwartz. J, J. Org. Chem., 1995, 60, 5963

B 0

(MeO)3SiH , LiOMe , ether

Ph

-20°C, 9h

*HOlph (8

+

XPh .

92) quant.

wth (Me0)$iI-I/HMPA/LiOMe/O°C/2h + (9O:lO) 98% Hojo, M.; Fujii, A.; Murakami, C.; Aihara, H.; Hosomi. Tetrahedron Lett., 1995, 36, 571

36

Compendium of Organic Synthetic Methods, Vol9

Section 42B

Hz (8 atm) , cat. RuClz(Binap)(dmf), -H

iPrOH , diamine , KOH ,28OC

d Ph Ph Ohkuma, T.; Ooka, H.; Ikariya, T.; Noyori. R,J. Am. Chem. Sot., 1995, 117, 10417

cat. [NiClz(PPh&

0

, cat. NaOH

OH 82%

- PhA iPrOH , Ar ,3Oh, heat PhA lyer. &; Varghese, J.P. J. Chem. Sot. Chem. Commun., 1995, 465

SECTION 42B: ALKYLATION

OF KETONES, FORMING ALCOHOLS

Aldol reactions are listed in Section 330 (Ketone-Alcohol)

o=

Me

/

0

Hebri, H.; Duiiach.;

e’ , SmC13, DMF , 20°C

Perichon, J. Tetrahedron Lett., 1993, 34, 1475 3 eq. Me$=CH2 , THF 0 -1OOC -+ rt

91% Hamett, J.J.; Alcaraz, L.; Mioskowski, C.; Martel, J.P.; LeGall, T.; Shin, D.-S.; Falck. J.K Tetrahedron Lett., 1994, 35, 2009

C6H13

-0.

JL

e’7 CH3

DMF , -OH Bu#BF4

+

.,,,330H OH

89% T,; Morishima, Y.; Moriyoshi, N.; Ishifune, M. J. Org. Chem., 1994, 59, 273

Section42B

Alkylation of Ketones

37

1.2.2 eq. SmI2 , THF 2 eq. t-BuOH

t

2. H30+

53% (1:l) &lolander. G.A,; McKie, J.A. J. Org. Chem., 1994, 59, 3186 0.05 CeC13,lh , THF 0

1.1

:=\ -MgBr

93% rtrov. V,; Bratavanov, S.; Simova, S.; Kostova, K. Tetrahedron Lett., 1994, 35, 6713

mBr C02Et

, In 91Oh CO2Et

aq. MeOH

Br9 wlust o=

76%

Ii. C.-k, Lu, Y.-Q. Tetrahedron Lett., 1995, 36, 2721

0

THF , 1Sh

1.8 Et$Zn , Ti(OiPr)4 , hexane

PhCHO Hang.;

80%

usescommercialZn dust Majee, A.; Das, A.R. Tetrahedron Lett., 1995, 36,&B

Ranu.;

OH

-23°C , 0.1 chiral catalyst Guo, C. Tetrahedron Lett., 1995, 36, 4947

Ph

Me3Ti*MeLi , ether W-h

97% 99% ee, S

w

-5OOC

Et

* W-h

selective for conjugated ketones in the presence of non-conjugated ketones M&& I&; Leung, C.W. J. Am. Chem. Sot., 1994, 116, 371

78%


38

Section42B

1. 10%CpzTi(PMe3)2,Ph#I-I2 1111111111

*

OH

6 >60%

Kablaoui, N.M.; Buchwald. S.L,J. Am. Chem. Sot., 1995, 117, 6785

e’ , MeCN , ZnBr2 Bu4N BF4

.

(95 Row

5) 85%

Y,; Derien, S.; DuWach,E.; Gebehenne,C.; Perkho;, J. Tetrahedron, 1993, 49, 7723

wBr *

+

Zn , aq. NH&l, THF

(54 Ahonen, M.; SiiSholm.

m’ PhL

..

46) 73%

Chem. Lett., 1995, 341

Ph

9PbCr(~eda) THF , -6OOC

Ph 77%

WiDf. P,; Lim, S. J. Chem. Sot. Chem. Commun., 1993, 1655

. 11.G,; Marcantoni, E.; Petrini, M. Angew. Chem. Int. Ed. En&

70% 1993, 32, 1061

39

Alcohols from Alkenes

Section44

SECTION 43: ALCOHOLS AND THIOLS FROM NITRILES 1. Li (excess), PhCHO , -3OOC + MeCN 5% 4,4’-his-t-Bu biphenyl 2. H20, HCl Guijarro, D.; Yus. M, Tetrahedron, 1994, 50, 3441

H 39%

Me-L

Ph

SECTION 44: ALCOHOLS AND THIOLS FROM ALKENES 1. Ti(BH& , 30 min CH2C12,-2OOC -2.10% K2CO3

c(,

+

aOH

1.2) 82% (1 Kumar, K.S.R.; Baskaran,S.; Chandrasekaran,S. Tetrahedron Lek., 1993, 34, 171 Me

Zn(BH& , DMF SiO2, rt ,30 min 30) 80%

(70 &nu. B.C,; Charkraborty, R.; Saha,M. Tetrahedron Lett., 1993, 34,‘4659

a

l.Mg*,THF,rt 2. ethylene oxide THF , -78OC 3. co2, oc + rt

OI-

0

a

OH 86% with Mg* = 8 Li, naphthalene,4 MgC12, THF, 3 Li H30+ at -78OC Sell, M.S.; Xiong, H.; We. R.D. Tetrahedron Lett., 1993, 34, 6007 6011 40°C 4. H30+ , 0°C + -9

o 69%

1.2 eq. Ph02BH, THF Nb catalyst, 25OC, Id 2. H202, NaOH Burgess.K,; Jaspars,M. Tetrahedron Lett., 1993, 34, 6813 also with CpzTiC14, see Burgess.K,; van der Donk, W.A. Tetrahedron L&t., 1993, 34,6817

40

Section 44


By 99% ee) 115, 12569

1993,

Hz, rt , lh , MeOWH20 RuC13,

TOA

TOA = trioctylamine Fache, F.; Lehuede, S.; LeMaire. M, Tetrahedron Lett., Ph 0 Cho, I.S.; Lee, B.; m

1995,

36,

99% (ciskans = 1.5) 885

[ (t-Bu2PH)Pd(Pt-Bu)2]2, H2 ,02 THF/CH2C12,6h


aq. Ba(OH), , NiAl(Raney alloy) 54%

60°C, lh

Br Br Tsukinoki, T.; Kakinami, T.; Iida, Y.; Ueno, M.; Ueno, Y.; Mashimo, T.; Tsuzuki, H.; Tashiro, M. J. Chem.Sot. Chem. Commun., 1995, 209 H2, [ W2(~&t’BU)6(@)2

1

Barry, J.T.; Chisholm.M.H, .I. Chem. Sot. Chem. Comma,

1995,

no yield 1599

74

Section 74B


SECTION

74B: Formation

of Aryls

OMe / LiCl , CuBr , inhibitor Pd(PPh& , dioxane , reflux

OMe &.& J.M.; MartoreU,G. J. Org. Chetn.,1993, 58, 1963

Crrissom, J.W,; Calkins, T.L.; McMillen,

bMe

H.A. J. Org. Chem., 1993, 58, 65% 50 at.mCO, AC@ PdCl2W’bh 9 mt3

PhooAc

PhH , 140°C, 3h Ishii, Y.; Gao, C.; Xu, W.-X.; Iwasaki,M.; Hidai. MJ.

C

*

OAc 69% Org. Chem., 1993, 58, 6818

HSiMe$-Bu , C) (50 atm) Ru~(CO)~~/PCY~, 140°C,20h

*

*:::: 45%

Chatani, N.; Fukumoto, Y.; Ida, T.; Murai.

S, J, Am. Chem. SM., 1993, 11.5, 11614

PhOH , PhMe ,180”C t

7h %

0

Danheiser, R.L,; Gould, A.E.; de la Pradilla, R.F.; Helgason, A.L. J. Org. Chem., 19%

5514

5%

Section 74B

75

Formation of Aryls

20% Ni(O)-PPh3 , HC=CH N---Ts THF,23OC, 12h 91% Sato, Y.; Nishimata, T.; Mori. M, .I. Org. Chem.,

1994,

59, 6133

1. PhNH2 2. Pd(OAc), , MeCN PhCHO B

;-;FHT3/

.

0

AQtZ

RamaRao.AV,; Reddy,K.L.; Reddy,M.M. Tetrahedron Lett.,

1994,

35,

5039

OH 1.5 I

y

~wipr)3

t

I

0.1SnC14, 0°C 1.5 (MeO)$iMe3

s 78% -Si(iPr)3

Angle. SR,; Boyce,J.P. Tetrahedron

Lett., 1994,

35, 6461

t-BuOOCOPh, Cu(OAc), CuBr , PhH , 80°C, 8.5h

56% Tavares,F.; Mevers. A.1, Tetrahedron Lett., 1994, 35, 6803 N-OH Bn

5% Pd/C, diethyleneglycol 188OC , diethyl ether, 45 min

Bn 89%

I Ar Ar = 4-methoxyphenyl Matsumoto.M.; Tomizuka,J.; Suzuki, M. Synth. Commun.,

1994,

24,

Al1441

76

Compendium

SECTION

74C: Alkylations

Section 74C


and Arylations

of Alkenes

2 BFjmOEt2 25OC

Maietich. G,; Zhang, Y.; Feltman, T.L. Tetrahedron L&t., 1993, 34,441 . Maretich. G,; Zhang, Y.; Feltman, T.L.; Duncan Jr., S. Tetrahedron Lett., 1993, 34, 445 Ar

/OH Ph Toluene , -45OC , 18h 2. LiEt3BH 3. MeOH 4. NaBH4

. Tomloka.;

Ar = 2,6-di-t-Bu-4-OMephenyl Shindo, M.; Koga, K. Tetrahedron

N

M

/

80%

(84% ee)

Lett., 1993, 34, 681

+3-l”l

H

DMF , BuflCl , ld 10% Pd(OAc)z ,3 iPr2NEt 66:34 E.-Z, 99% 5 HC02Na Ding, S. Tetrahedron Lett., 1993, 34, 979

%

0

Larock.;

w-4

1

Me

cat. Pd(OAc);? , Ag2C@ DMF ,45OC, overnight

C02Me Wll

OH OH &ff@.

T, Tetrahedron

L&t., 1993,

34,

1133

NH2

75%

Section 74C

Alkylation of Alkenes

77

Me

1. Et&Cl

60% 2. BuZnCl , DMF * BuJ==i OH 5% C12Pd(PPh3)2 2 BuLi ,5h Ay, M.; Gulevich, Y.V.; Noda, Y. Tetrahedron Lett., 1993, 34, 1437 OH

. . Nenlshl,;

0

SnBu3

v

10h

Zhang, H-C.; Brakta, M.; DavesJr,. G.D, Tetrahedron

OTf

0

0

L&t., 1993, 34, 1571

, 30°C, 91h 58% 87%ee,R

Pd(R-BINAP)2, PhH ProtonSponge C)zawa.F,; Kobatake,T.; wi.

Pi0

x

T, Tetrahedron Lett., 1993, 34, 2505

Q-I 11I, AIBN , To1 52%

46h, 85OC

SnBu3 Kinnev. W.A, Tetrahedron Lett., 1993, 34, 2715 PhBr , To1,2% Pd(PPh& phm,, Bu$nmNI-12 R.J&; Geng,B.; &Iore;ill. J.JE J. Org. Chem., 1993, 58, 1443 w-h7

00

w-b3

1. Me2SCHC02Et

H

Bu$n

B(W

l312

2. H202, NaOAc

Dem. M.-Z,; Li, N.-S.; Huanrr.Y.-Z,J. Org. Chem., 1993, 58, 1949

60%

47%


Section 74C

0

Br J&;

OMe

Qabar, M.N. J. Org. Chem., 1993,

58, 4473

1. PdC12 , LiCl , THF o”c + 25OC ] 2. aq. NH4Cl

-PhINH2

0

2. PhHgCl , O2 60% Larock. R.C%; Ding, S. J. Org. Chem., 1993,

E:z)

58, 2081

PhOTf , Pd(PPh3)4, 85OC

(CH2)8co2Me

/9-BBN

/

(74:26

&PO4 , dioxane

-

ph-

58,

2201

(cH2)&02Me 87%

Oh-e, T.; &G\raura. N.: Suzuki. A, J. Org. Chem., 1993, Ph

1.2 Et$n , 1.5% PdC12(dppf), THF 2. CuCN.2 LiCl 3.

Stadmiiller, Sot., 1993,

C02Et

H.; Lentz, R.; Tucker, C.E.; S tiidemann, T.; Diirner, W.; Knochel. 115, 7027

phi

3 eq. EtMgBr , Cp$rCl2 THF,rt,6h

Suzuki, N.; Kondakov,

D.Y.; Takahashi,

T, J. Am. Chem. Sot., 1993, 11.5, 8485

J. Am. Chem.

Section 74C


79

C02Et N2+BFd

4

C02Et

, EtOH

2% Pd(OAc)z , 60°C, lh

SenguPta.;

Bhattacharyya, OH

71%

S. J. Chem. Sot., Perkin Trans. l., 1993, 1943 OH

5 eq. MeMgBr 0.05 PdC12(PPh3)2

97% VW,;

Giesen, V.; Fuest, M. Liebigs Ann. Chem., 1993, 629

e, , DMF , Et&104 47% Ni(teta)(ClO& Ozaki. S,; Horiguchi,

I.; Matsushita, H.; Ohmori, H. Tetrahedron

Lett., 1994, 35, 725 iMe

LDA, TMS-Cl C3H

06

Et Wright. S.W, Tetrahedron

THF , -78OC

*

C3H

Et

93%

Lett., 1994, 35, 1841 Phi , Bu4NHS04,

aq. MeOH

02Me

02Me 5% [Pd(OAc)2/2 PPh3] Jeffery. T, Tetrahedron

A Ph

96%

Heck reaction in aqueous media Lett., 1994, 35, 3051

0

0

Phi , SmIz/THF , 15 min DMSO

0 Nazareno, M.A.; Rossi. R.A, Tetrahedron

Ph A/ Lett., 1994, 35, 5185

Ph

47%

Compendium


Section 74C

Ph Pd(OAc)2, Bu3P, 3h IS2CO3 , DMF , 80°C +

Phi

Ph +

quant. (78 Ono, IS.; Fugami, K.; Tanaka, S.; Tamaru. Y, Tetrahedron Lett., 1994, 0

I

Majetich.

OOCNHMe 6) 35, 4133

0 2 AlEt

, 0°C b

SPh

10h

G,; Zhang, Y.; Liu, S. Tetrahedron

SPh

I

0 Lett., 1994,

4 35,4887

0

70%

,SnBuj

Pd(PPh3)4, THF ,65OC, lh Matthews,

D.P.; Waid, P.P.; Sabol. J.S.: McCarthy. J.R, Tetrahedron

66% Lett., 1994, 35, 5177

TfO OMe

SnBu3

OMe 70%

B.

D,; Cardamone, Rbe9 Guzzi, U. Tetrahedron l

/ SnBu3 1. 5% Pd2(dba)3 ,20% AsPh3 w 2.5% TFA , CH2C12 = Rink amide resin Deshnande. M.S, Tetrahedron

Lett., 1994, 35, 5613

89%

Section 74C

81


2 eq. MesSiCHzMgCl

phwseMe

b l?h-siMe3 5% NiC12(PPh&, DME reflux , 1.5h Hevesi.L,; Hermans,B.; Allard, C. Tetrahedron Left., 1994, 35, 6729 1.0.3 q3-C3HSPdC1)2 , HSiPh2F 0.6 o’-diphenylphosphinobinaphthol Ph-

79%

Ph

derivative

P

20°C , 10h 2. MeLi

Me S iPh2Me

96% (66%ee,S) Hatanaka. Y,; Goda, K.; Yamashita, F.; Hiyama, T. Tetrahedron

NC

/‘Q

Left., 1994, 35, 7981

0

NH 12

NH2

Mn(OAc), , CuOAc ultrasound ,4h

/ Bosman, C.; D’Annibale.

0

47%

A.; Resta,S.; Trorrolo.C, Tetrahedron Bufl+

Left., 1994, 35, 8049

(Ph3SnF2)‘, THF

OTf

Ph Pd(PPh3)4, reflux ,30 min

-

8-

81% A.&; Barcina, J.O.; Cerezo, A. de F.; Subramanian, L.R. Synlett, 1994, 1047

10% ZrC12(qC&),

1.5 BuMgCl

II, 6h Takahashi. T,; Kotora, M.; Kasai, K. J. Chem. Sot. Chem. Commun., 1994, 2693 ,SiUe3 1. BuLi , THF , -7OOC 2.ZnBr2, -7OOC + 2o”c 3. H30+

t

81%

82

Section 74C


C$-I&Me#H

, Et3SiH

t

AcH$(H$)4\/

SW3

tridecane , di-t-Bu hyponitrite 65% Dang, H.-S.; Roberts,.P,

Tetrahedron

Lett., 1995, 36, 2875

PhSnCl3, aq. KOH ,3% PdC12 *

Br*COOH

Ph*COOH 83%

Rai, R.; Aubrecht, K.B.; Collum. D.B. Tetrahedron

Lett., 1995, 36, 3169

cylization-Diels-Alder

Joumet, M.; B.

m J. Org. Chem., 1995, 60, 6885

Chavan. S.P,; Ethiraj, KS. Tetrahedron

Lett., 1995, 36, 2281

OMe

OMe BF3eOEt2, C&I 12, refk

y 2h

56% Maietich.

G,; Liu, S.; Siesel, D. Tetrahedron

Lett., 1995, 36, 4749

Alkylation

section 74C

83

of Alkenes

Ph 10% Pd(OAc)z ,20% Bu3P Phi , DMF, 100°C, 1Sh

S.-K,; Jung, K.-Y.; Park, C.-H.; Namkoong, E.-Y.; Kim, T.-H. Tetrahedron

Zhang, W.; Dowd. P, Tetrahedron

Lett., 1995,

Lett., 1995, 36, 8539

95% Yu, J.; Cho, H.S.; Falck.

Tetrahedron

Lett., 1995, 36, 8577

. JEt3

, PhMe , reflux

5% RuH2(CO)(PPh& 94% Trost.;

Ixni, K.; Davies, I.W. J. Am. Chem. Sot., 1995, 117, 5371 1. Me3Al,8%

y”

Cl$ZrCpz , DCE ,22OC

2.02 92% (74% ee)

Kondakov,

D.Y.; Negishi.J.

Am. Chem. Sot., 1995, 117, 10771

Compendium of OrganicSyntheticMethods,Vol9

84

4

OTf

Draper,T.L.; mv.

Section74D

CO,Et

,5% PdC12(PPh3)2 w 3 LiCl , DMF , 110°C

T&SynZett, 1995, 157 Si(OEt)g

Si(OEth

, toluene,135OC

0

0

Ru(H)2(CO)(PPh&7 2d

%

c

50% Kakiuchi, F.; Tanaka,Y.; Sato,T.; Chatani,N.; Murai. S, Chem. Lett., 1995,

679

1. BC13, CH2C12,O°C PhwPh 2. catechol, PhH 3. PhBr, Pd(PPh& , NaOH Farinola,G.M.; Fiandanese, V.; Mazzone,L.; Naso.F, J. Chem. Sot. Chem. Commun., ph-sMe3

86% 1995,

2523 REVIEW:

“RecentDevelopments andNew Perspectives In The HeckReaction,”Cabri.W,; Candiani,T. Accts. Chem. Res., 1995,

SECTION

74D:

28, 2

Conjugate Reduction of a&Unsaturated Carbonyl Compounds and Nitriles

0

0

2% [Pd(Pt-Bu)(PHt-Bu& 02 9 H2(10 psi) I 4

Me

90%

THFJ3h glassautoclave )

Sommovigo,M.; u.H.Tetrahedron

Lett., 1993,

4

Me

34, 59

OH Eta-

9 ~&oh6

t

ph/\/co2ph

CO (1 atm), NE@,3O”C 80%

bh. x; Fujiwara,IS.; Takahashi,S. Bull. Chem. Sot. Jpn., 1993, 66, 978

Section 74D

85

Conjugate Reduction

PhSiH3, 20°C, 16h MOcomplex

..

(62 Schmidt.T, Tetrahedron

38) 95%conversion

Lett., 1994, 35, 3513

NaHTe, EtOH Ph*CHO

w

phmCHO

rt ,5h

>98%

Yamashita.M,; Tanaka,Y.; Arita, A.; Nishida,M. J. org. Chem., 1994, 59, 350 TFA-Et3SiH,30 min -78°C + O°C

zhao, Y.; m.

variousprotonicandLewisacidsused P,; Keo, E.A. Tetrahedron Lett., 1994, 35, 4179

NH4+HC02-, Pd-C

t

25OC,4h

Ranu.B.C; Sarkar,A. Tetrahedron

Lett., 1994, 35, 8649

Bakersyeast, 31°C =, pheNo2 phmNo2 3d . shl&, M..; Yoshida,S.; Kohno,Y. Heterocycles, 1994,37, 553

43%

limonene, 10%Pd/C, reflux 0

o= von Holleben.M.L,; Zucolotto,M.; Zini, C.A.; Oliveira, E.R. Tetrahedron,

0

quant.

o=

6994, 50, 973


86

Na&Od

, aq. dioxane

,5O”C

PhA

, lh *

ECHO

Section 74E

Phi

ICI-IO selective

reduction

of conjugated

Dhillon. RS,; Singh, R.P.; Kaur, D. Tetrahedron

carbonyl C=C units L&t., 1995, 36, 1107

Sm, 12, MeOH , 1min t Bessho,K.; Yanada,K. Synlett,

a;

C02Me

ph/\/C02Et

97% 1995,

443

C02Me

BER-CuS04, MeOH, rt

BER = borohydrideexchangeresin Sim, T.B.; Yoon. N.M,SynZett,

1995,

94%

726

NaBHeBiC13,95%EtOH t

wC02Et Ren,P.-D.; Pan,S.-F.; Dong, T.-W.; Wu. S.-HJynth.

-

CO2Et 98%

Commun., 1995, 25, 3395

0

0

Bakersyeast

,; Saitou,K.; Hida,K.; Ohno,A. Tetrahedron

SECTION

Asymmetry, 1995, 6, 2143

74E: Conjugate Alkylations

Ranu. B.c; Saha,M.; Bhar, S. Tetrahedron

L&t., 1993, 34, 1989

Section 74E

Conjugate Alkylations

PhS-

b

0’ Li+

EL CH2C12 2d, -78OC

\ 6

‘t,

CO2Me

87

C02Me

6

SPh + 2

(15 Corey. E.J,; Houpis, I.N. Tetrahedron

Lett., 1993, 34, 24k

P 1. PhMgBr , CuBr*SMez

h Tv

2.NBS,THF,-78°C

*

0

Li, G.; Jarosinski,M.A.; J-In&y. V.J, Tetrahedron Lett., 1993, 34, 2565 0

PhguLi , THF , -78OC + TMSCl + TMSCN ; James,B. Tetrahedron

81% 83%-k

Ph

Lett., 1993, 34, 6689

h

3 eq.mSnBu3 0.05(Bu$n)z 6 eq.PhSCH(OMe)z 0.3 M PhH, hv (sunlamp)

ea

20%

Me

69%

OMe

(8: 1 transxis)

mk. G&; Kordik, C.P. Tetrahedron Lett., 1993, 34, 6875

I

1

Me(Boc)NCHzSnBu$s-BuLi TMEDA , CuCN, TI-IF

er. m;

Alexander,C.W. Synlett, 1993, 407

&

98% NMeBoc

Section 74E


88

Et

$

Et 9 Eu( tfc)3 MS , Ccl,, -33OC, 72h

-*

71% (25%ee)

Eu(tfc)3 = [tris-(3-trifluoromethylhydroxymethylene)-d-camphorato] europium (III) Tetrahedron L&t., 1993, 34, 7649 Bonadies, F.; Lattanzi, A.; Orelli, L.R.; Resci, S.; Screttri.

1. BnOCH~CH+CH/Cp$Zr(H)Cl 2. MeLi , Me$u(CN)Liz

81% rnshutz.R.H; Wood, M.R. J. Am. Chem. Sot., 1993, 115, 12625 0 -3

1. Ni(aca& 2. -w

80% Eshelby,J.J.; Crowley, P.J.; Parsons.P.J,Synlett, 1993, 279 1. Me2CuLieLiI

Bu

-

/-co2Et

*

2. MeOTf Amdt, S.; Handke,G.; Krause.N, Chem. Ber., 1993, 126,251

4

SO2Ph -

1. t-BuBr , Cr(en)2+2 , DMF ,4h * 2.H20

t-Bu \

78% \

en = ethylenediamine Tashtoush,H.I.; hstmann. R, Chem. Ber., 1993, 126, 1759

S02Ph

Section 74E

Conjugate AIkylations

89

Ph$b , cat. Pd(OAc);! 0

AgOAc , AcOH ,25OC

Cho, C.S.; Tanabe, K.; Uemura.

Tetrahedron

Ph

Lett., 1994,

0

1275

35,

41%

3 eq. SmI2,THF ,-78°C

Trivellas,A. Tetrahedron Lett., 1994, 35, 1627

-E.J.;

cat. Pd(OAc)z, NaOAc , Id cat. SbC13,AcOH ,25OC *

‘“\(‘rf

88%

0

Ph Cho, C.S.; Motofusa, S.; IJemura.S, Tetrahedron Lett., 1994, 35, 1739 r

0

Me02

3 eq.Me$iSnBu3,2 eq.CsF DMF,rt, lh Br Sate,H.; Isono,N.; Okamura,K.; Date,T.; Mori. M, Tetrahedron

Lett., 1994, 35, 2035

MeTi(OiPr)dMgCl , TI-IF Ni(acac)z, -15OC + rt

Bs.; 6075

.

85%

Kabbara,J.; Nickisch,K.; Neh, H.; Westermann, J. Tetrahedron Mt., 1994, 35,

90


Section 74E

t-BuHgCl , Et3SiH , DMSO ==c

) dark, hv (sunlamp) -35OC , llh Russell. G.A,; Shi, B.Z. Tetrahedron Lett., 1994, 35, 3841 C02Et

Et$i

A

C02Et 93%

iPrCH0, LiNO3, aq.MeCN e’ C02Me +QL 2 34% UT.; Soejima,T.; Takigawa,K.; Yamaguchi,Y.; Maekawa,H.; I(ashimura. S, Tetrahedron Lett., 1994, 35, 4161 Y

C02teBu 1. BuLi, m -100°C + 3o”c

,C02t-B :: = t =

2. H-20

u

70% +

otherisomers

CookeJr.. M.P,; Gopal,D. Tetrahedron

Lett., 1994, 35, 2837

PhCHO, Ph2C0 hv

Kraus.G.A,; Liu, P. Tetrahedron

69%

Lett., 1994, 35, 7723

MeMgCl , CeC13,THF

Bli.

G,; Bosco,M.; Sambri,L.; Marcantoni,E. Tetrahedron Lett., 1994, 35, 8651


Section 74E

wey.

a, Hajra, S.; Ghorai, M.K. Tetrahedron

91

Lett., 1994,

35, 7837

MeO&

Bu$nH

COzMe

.

(1 Miura,

Iondo, T.; Hosomi. A, Tetrahedron

0

$

+

, PhH

BuC=CH , PhC=CSnEtj

Wl

W-I

11

1) 54%

Le ‘tt., 1;94,35,9605

, Me&Cl

Ni(acac)z , Dibal , THF , rt ,2h

%A

80% (>95:5 E.-Z) Ikeda, S.; &to.

Y, J. Am. Chem. Sot., 1994,

116,

5975 CHO

I

94% (93:7 1,4: 1,2) Kabbara. L; Flemming, S.; Nickisch, IS.; Neh, H.; Westermann, J. Synlett, 1994, 679 Et2Zn , MeCN , 1.5% NiC12 , -3OOC phL

ph

309’ chual pyrrolidine 0

l

*Phuh 75% (82% ee , S)

Asami. MJ Usui, K.; Higuchi, S.; Inoue, S. Chem. L&t., 1994,

297

Compendium

92

Ph

Section 74E


Z

Li

Y CH2CI;!

99% AI(OAr)3 , -78OC , lh

I

Ar = 2,5diphenylphenyl Maruoka,

Ph

K.; Shimada, I.; Imoto, H.; Yamamoto. H, Synlett, 1994, 519 PhMezSi

0 HSiPhMe2 , toluene , 1 10°C A

-N

*

[Rh2(oAc),l

dNJl

I I Bn Bn u T,; Oda, T.; Kimura, F.; Onishi, H.; Kanda, T.; I(;ito. S, J. Chem. Sm. Chem. Commun., 1994,2143 1. PhMe#Li ph&C02Me

Crump, R.A.N.C.; wing.;

87%

, Me$Zn , THF/toluene , O°C

2* aq* NH4C1

CO2Me

98% 73% using cuprate Urch, C.J. .I. Chem. Sot., Perkin Trans. l., 1994, 701

5% CuBr , THF , TMSCl ,4h AlMe

, 10% solution in hexane

96% Kabbara. J,; Flemming, S.; Nickisch, K.; Neh, H.; Westermann, J. Chem. Ber., 1994, 127, 1489 t-Bu

t-Bu (t-Bu)2Cu(CN)Li2

t-Bu w

C02Et Gerold, A.; .Krause. N, Chem. Ber., 1994, 127, 1547

quant. 111111111 \ CO2Et

Section 74E


93

0

, DME ,0.3h

-A

C02Et

B

.

LiOH , Hz0

96% FJ Forcellese, M.L.; Locati, L.; Screttri, A.; Scolamiero, C. Guzz. Chim. Ital., 1994,

124,467

PhBr, NiBr2, e’ *

-/c”u

63%

phwco2Et

3 H20, DMF-Py , 80°C Bumr , Bu&I Condon-Guegnot&; Leonel,E.; N&l&ec, J.-Y.; P&ichon,J. J. Org. Chem., 1995, 60, 7684 OSiMe3

0 5 M LiClOd, ether

Sarawathy,V.G.; Sankararaman.J.

70% Org. Chem., 1995, 60, 5024

t-BuZnBr , THF/pentane, -3OC 2 TMSCl , 1.5BF3aEt2 Hanson,M.V.; Rieke,

J. Am. Chem. Sot., 1995, I 17, 10775

iPr1, Bu$nH , Yb(OTf)3

t

CH2Q/hexaneKHF . . Slbl. M&; Jasperse, C.P.; Ji, J. J. Am. Chem. Sot., 1995, II7, 10779 neatAl(C3H7)3,5% CuBr Ph& w;

Flemming,S.; Nickisch,K.; Neh, H.; Westermnn,J. Tetrahedron,

76% 1995, 51, 743

94

Section 74F


1. &D

,O”C,hv

2. LTA , PhH , heat

Barton, D.H.R.; Chem, C.-Y.; Jaszberenvi. JCs, Tetrahedron,

1995,

C02Me 98~25% 51, 1867

R.-S)

61%(80%ee;10:90

Wu, J.H.; Radinov, R.; Porter. N.A, J. Am. Chem. Sot., 1995, 117, 11029 REVIEW:

“Intramolecular MichaelandAnti-MichaelAdditionsto Carbon-Carbon Triple Bonds,”Rudorf, W.-D.; Schwarz,R. Synlett, 1993, 341 SECTION

74F:

Cyclopropanations, SO2Ph

including Halocyclopropanations

‘CH(SOMe)2,DMSO 99% 20°C, 15min

J-E,; Lofstom,C.; Juntunen,SK. Tetrahedron Lett., 1993, 34, 2007 N2CHC02t-Bu, CH2C12

/,%, + ,,\+\’A *,%, ‘Cod-Bu ‘h ‘C02t-B u . (86 . 14) 75% 92%ee Ito, K.; Katsuki.T, Tetrahedron Lett., 1993, 34, 2661 CuOTF-biarylamine ligand -,PP

C&I, CrCl$Fe

02Et C02Et

Hu. C-M.; Chen,J. Tetrahedron

Lett., 1993, 34, 5957

89%

Section 74F

Cyclopropanations

95

70%

\ Kreif. A; Dubois, P. Tetrahedron

Lett., 1993, 34, 2691

Ph

P Bu$nN(Et)CO2Me,DCE

(93:7 1,2-tranxcis) Shibata,I; Mori, Y.; Yamasaki,H.; Baba,A.; Matsuda,H. Tetrahedron Lett., 1993, 34, 6567

Ph

h

bis-Rh catalyst, styrene

t 0 . Davies.;

L4 = = Eo,?Me

63% Hutcheson,D.K. Tetrahedron

Ph +

9O%ee

Lett., 1993, 34, 7243

1.NBS, DMSO ,5 min ,,il/v/

::::;:H

*

p Kd’

Dechoux,L.; Ebel, M.; Jung,L.; Stembach.J.F, Tetrahedron

L”ToEt 10%Pd(PPh3)4,DMF ,7h

)

H g2%

(>99: 1 cis:trans)

Lett., 1993, 34, 7405

;

0 Ogoshi,S.; Morimoto, T.; Nishio, K.; Ohe, K.; Murai. S,J. Org. Chem., 1993, 58, 9

gg%

96


..

(97

.

Section 74F

3)

84%

avres.H.ML; Huby, N.J.S.; CantrellJr., W.R.; Olive, J.L. J. Am. Chem, Sot., 9468

1993,

115,

CrC12- DMF ,3h Bu

CHO 32%

Montgomery,D.; Reynolds,K.; Stevenson.P,J. Chem. Sot. Chem. Commun., SO2Ph

LiCH(SPh)S02Ph,THF

/

SPh

-78OC + O°C

t

1993,

363

PhS Isc-

81% Bailey, P.L.; Hewkin, C.T.; Clegg,W.; kkson. R.F.W, J. Chem. Sot., Perkin Trans. I., 1993,577

Me I

0-

C@Me

Na+%H(C02Me)2,TI-IF-HMPA -70OC + O°C ,3h

C02Me 63%

Watanabe,Y .; Ueno,Y .; m.

T, Bull. Chem. Sot. Jpn., 1993, 66, 2042 CH212,Zn , Et20 40°C, 8h Pb , Me$iCl

SK.;

Kakiuchi,T.; -0.

Ic J. Org. Chem., 1994, 59, 2671

97%

Section 74F

Cyclopropanations

97

PhS,

b @Ylr::~~~: 302Me Mac 50%

C02Me

Denis,R.C.; Gravel. D, Tetrahedron Lett.,

35, 4531

1994,

(2.7 OH

Bu$n ai

2 eq.Et@, CH& CH$lz-hexane, -2OOC NHSO&H,pNo,

0

BGn, -

%, /

#H ++

HA_

OH

+ NHS02-C6H4p-NO2

86%ee(2S,3R),94% Imai, N.; Sakamoto,K.; Takahashi,H.; Kobavashi,S, Tetrahedron Lett., 1994, 35, 7045 1. PhCHN2 2. PhCH=CHz, rt , 12h

cp\ OC-Fe/ oc

-4

Seitz, W.J.; Hossain.M.M, Tetrahedron

80% (96:4 cixtrans) Lett., 1994, 35, 7561

MezN

Ph

&pNMe2 + “)7

1. PheOH

Ph

0\/

0 B Bu

w PhvOH

2.2.2 Zn(CH21)2 >95%(29:1)

Charette.A.B,; Juteau,H. J. Am. Chem, Sot., 1994, 116, 2651 Et$n , CH212,CH& hexane, -2OOC

Ph a

Ph-oH

Hs s: a H

,SO,Ph

OH

N\ ,B-iBu N ‘SO

quant.(76%ee) Ph

Imai, N.; Takahashi,11.;Kobayashi.S, Chem. Lett.,‘1994,

177

98

Compendium


Section 74F

Ph Ph ’ Br

Ph

Bu2Te@mSiMe

3

0 +

C&03, 7o”c DME , trace water

Ph

Me3Si

Y.-z;

..

8) 93% MesSi Tang, Y .; Zhou, Z.-L.; Xia, W.; Shi, L.-P. J. Chem. Sot., Perkin Trans. I .,

1994,893

3-pentanone/LDA ,

THF

*

S02Ph Ericsson, A.M.; Plobeck, N.A.; mkvall.

62% J.-E. Acta Chem. Stand. B., 1994, 48, 252

Zn ClMe2SiCH$H$iMe2Cl

Mo(.herwell.

W.B,; Roberts, L.R. Tetrahedron

L&t., 1995, 36, 1121

2 Ti(OiPr)d 4 iPrMgBr -45OC +

0°C 93% (58:42

Kasatkin, A.; Sate.

PhaOH

Tetrahedron

Lat., 1995,

36,

trans:cis)

6079

l.Zn(CH$)2 2. -78OC -+ -2OOC 3. TiQ

*

ph-YoH 90%

Charette.,

Brochu, C. J. Am. Chem. Sot., 1995,

117, 11367

Section 75

Alkyls from Misc.

99

5% semi-corrin Cu complex , DCE 23OC

57% (95% ee) Pique, C.; Fahndrich, B.; pfaltz. A, Synlett, 1995, 49 1 1. XX12 , CC14, reflux 2. NaI04 , 0.1 RuC13

85%

3. Li 5% DTBB , THF 4. H20 Guijarro, D.; Yus. w Tetrahedron,

Ar

Ar = 4- t-bu tylphenyl 1995, 51, 11445

REVIEW:

“The AsymmetricCyclopropanantion of Acyclic Allylic Alcohols:Efficient Stereocontrol with IodomethylzincReagents,”w. A&; Marcoux, J.-F. Synlett, 1995, 1197

SECTION

75:

ALKYLS, METHYLENES AND ARYLS MISCELLANEOUS COMPOUNDS

~co2MhMe#-~-~~2~(OAc)~

as.

.

LEMe

Y,; Planchenault, D.; Weber,V. Tetrahedron Lett., 1994, 35, 9549

SOzt-Bu

FROM

73%

Ph

2 PhMgBr,5% NiC12(PPh&

77%

Clayden,J.; Cooney,J.J.A.; Julia. M cJ. Chem. Sot., Perkin Trans. 1.) 1995, 7 REVIEW:

“OrganonickelChemistryin OrganicSynthesis.SomeApplicationsof Alkyl and MetalacyclicDerivatives,”C&npora,J.; Paneque, M.; Poveda,M.L.; Carmona.E. Synlett, 1994,465


100


CHAPTER

6

PREPARATION

SECTION

Section 77

OF AMIDES

76: AMIDES

FROM ALKYNES 0.3 Iu1&0)16, co, Hz0 dioxane , NEt3 , 175OC Ph Ph

Hirao, K.; Morii, N.; Joh, T.; Takahashl. . S, Tetrahedron

SECTION

77: AMIDES

FROM ACID DERIVATIVES 1. SnFJ(TMS)2]2

OH Bumell-Curty,

2.

C

C.; lXosw Tick,

Lett., 1995, 36, 6243

, THF , rt Pa

NNH

‘N

7 14h

a

89%

Tetrahedron

Lett., 1993, 34, 5193

Li , Me3SiCl CsF’N2

)

+

pANH

iplq.ll

2

Kawaguchi,

C&I17NH2, W-J

17CWH

0

180°C, 30 min t C8h

. SIC. B&;

H

77% M.; Hamaoka, S.; Mori. M. Tetrahedron L&t., 1993, 34, 6907

NHC8H17

98% Zdravkovski,

2. Synth. Commun., 1993, 23, 2761

11%

Section 78

Amides from Alcohols

101

Cl

Ph

NMM , PhCl , mrcrowave *

f

N\

75OC ,2 min

Me

.

(20 Bose, AK.; Banik, B.K.; Manhas. MS, Tetrahedron

80) no yield

Lett., 1995, 36, 213 Ph

PhCH-NPh , toluene , Bufl 40% (5:95 cis:trans) Ph Browne, M.; Burnett, D.A.; Caplen, M.A.p; Chen, L.-Y.; Clader, J.W.; Domalski, M.; Dugar, S.; Pushpavanam, P.; Sher, R.; Vaccaro. W,; Viziano, M.; Zhao, H. Tetrahedron Lett., 1995, 36,2555 -C02H

,CWl;!

‘z ;;iPPb

. Frayen. P,Synth.

t

bCONHBn

2

98%

Commun., 1995, 25, 959 1. NsCl , NEt3 , DMAP/MeCN

, rt

0

+

PhCOOH 2. PhNH;! , rt

NHPh

Is,e. JC,; Cho, Y.H.; Lee, H.K.; Cho, S.H. Synth.Commun.,

SECTION

78: AMIDES OH

FROM

ALCOHOLS

1995, 25, 2877

AND THIOLS

CoC12, Ac20, MeCN *

Mukhopadhyay,

M.; Reddy, M.M.; Maikap, G.C.; w.

-(=)-/OH

MeCN , BFyOEt2

Firouzabadi.

LNHAc

J, J. Org. Chem., 1995, 60, 2670

w-

H,; Sardarian, A.R.; Badparva, H. Synth. Commun., 1994, 24, 601

92%

102

Section 81


SECTION

79: AMIDES

FROM

ALDEHYDES

NO ADDITIONAL EXAMPLES

SECTION

80:

AMIDES ARYLS

‘-(=)

FROM

ALKYLS,

PPA , AcOH , NH20H*HCl

METHYLENES

AND

‘-0

*

llO°C , 14h

80% Cablewski,T.; Gurr, P.A.; Raner,K.D.; S

SECTION

81: AMIDES

FROM

Org. Chem., 1994, 59, 5814

C&J.

AMIDES

Conjugate reductions of unsaturated amides are listed in Section 74D (Alkyls from Alkenes).

oJ-q// 1,,,,,,, A H

Wei, Z-Y.; Knaus.

Tetrahedron

Lett., 1993, 34, 4439

2.1 TBSOTf ,23OC 4.2 NEt3 , 1.75h

Ph J

R *

N/ I

Phd/Me

Me 75%

2.1 TBSOTf ,23OC 4.2 collidine ,2h

&&

91% (>99%ee)

MeOH

H

Ph

J 49%

G.E.; McHardey,S.F.; Murry, J.A. Tetrahedron

PhI(OAc)2,

A! I

KOH

N/

Me

I

cH2oTBs

Lett., 1993, 34,6215

72% NHCO2Me

Vaid, R.K.; P&ash, 0.; Tuladhar,SM. J. Org. Chem.,

Section 81

Amides from Amides

PhMgBr , THF

OEt H Wei, Z.Y.; Knaus.

A

Ph

103

H

78%

Org. Prep. Proceed. Int., 1993, 25, 255

1. 2 eq. s-BuLi, (-)-sparteine NHMe 2. Me1

Beak. P,; Du, H. J. Am. Chem. Sot.,

1

NHMe 84%(78%ee)

1993,

115, 2516

0

4.2 eq.CuBrz*LiOt-Bu

77%

*

Ph rt ,6h NH2 Yamaguchi,J.; Hoshi,K.; Qkgla. T, Chem. Lett.,

5) c>, 0

1993,

PhHNJL

Ot-Bu

1273

, acetone, O°C

CL N N 0 I I H OH Nesct,S.M.; Benneche,T.; Undheim,K. Acta Chem. Scand. B., 1993, 47,

71% 0 1141

CF3S03H, CH2C12 H

0.75h , 20°C

m

C.&l,; Fallah,A. Tetrahedron

&-H

Lett., 1994, 35, 293

DkE

*

4-K;

DIAD = diisopropylazodicarboxylate 0 Ww.

M.A. Tetrahedron

Lett., 1994, 35,665

91% (+ 4% lactone)

104

Compendium


Section 8 1

1. Br;! 2. NEt3 3. BnNH2

n B N

4. Mg(OMe)z

tier.

P,; Dogan, 0.; Pillai, S. Tetrahedron

H

Lett., 1994, 35, 1653

Axon, J.; Boiteau, L.; Boivin, J.; Forbes, J.E.; md.

Hoffman.V,; 35,323l

(s)

*Y 86x79%

1. (PhCO)zO , PhH , reflux 2. Bu$nH , AIBN , PhH

BnI-IN

P

, MeOH

02Me

Me

67%x”high yield” Lett., 1994, 35, 1719

SZ, Tetrahedron

iPrOH , 80°C, lh

d I OTf Nayyar, N.K.; Shankweiler,

CH20iPr 85%

J.M.; Klinekole

H III, B.W. Tetrahedron

C7H &HO, Hz, 40 bar Pd/C-Na2S04, EtOAc

0

0

1ooOC H Fache, F.; Jacquot, L.; J,eme.

Ph-NVCI

93%

w17

M, Tetrahedron

L&t., 1994, 35, 3313

s-BuLifIMEDA I Boc

Lett., 1994,

, THF

a

Ph 4

-78OC, 5h

Beak. P,; Wu, S.; Yum, E.K.; Jun, Y.M. J. Org. Chem., 1994, 59, 276

N I Boc

82%

Section 81

Amides from Amides

105

PhCHO , PPE , 60°C, 16h

H N’

51% * I PPE = polyphosphoric ester ci Ph Marson. CM,; Grabowska, U.; EaIlah, A.; WaIsgrove, T.; Eggleston, D.S.; Baures, P.W. J. Org. Chem., 1994, 59, 291 NH2

S Me N’

1. 1.3 eq. POC13,

-78OC

2.3.5 eq. TM&S

, -78OC +

Me N’ rt ,4h

91%

* c ei Smith, D.C.; Lee, S.W.; Fuchs. P.L, J. Org. Chem., 1994, 59, 348 0

0

BnNH2, AlC13 , 90°C >

NHBn

NH2

67% Bon, E.; Bigg. D.C.H.: Bertrand. G, J. Org. Chem., 1994, 59, 4035

yx N I

1.2 s-BuLi/2 TMEDA THF , -78OC, 8h Ot-Bu

2. BuI

CH3

Snieckus. V,; Rogers-Evans, M.; Beak. P,; Lee, WK.; 1994, 35, 4067

0 -Y

A N Ot-Bu I CH2Bu 70% Yum, E.K.; Freskos, J. Tetrahedron L&t.,

Bu$nH , cat. AIBN (addn over 4 h) degassed cyclohexane -

(Do

Ph Callier, A.-C.; Quiclet-Sire,

B.; Zard. S.2, Tetrahedron

66% Lett., 1994, 35, 6109

\

Me

106


Bu$nH,

Section 8 1

AIBN

PhH (OSM) Keusenkothen,

P.F.; Smith. M.B, J. Chem. Sot., Perkin Trans. I., 1994, 2485

Ts I N

iPrMgC1, THF , O°C ,6h

/\

4J4 *‘Ph

. . oshlmuu. 3465

. 57) 63% (45 A, ; Abe, H.; Hirosawa, C.; Tamao, K. J. Chem. Sot., Perkin Trans. I., 1994,

anek- E,; Wuonola,M.A.;

NH2

Harlow, R.L. J. Heterocyclic

65% x low yield Chem., 1994, 31, 1251 H I NN

1. B tCH20H

2. CH2=CHCH2SiMc3 BF3eOEt2 63% 0 R... menko. A.V.. . La n g. H, J. Org. Chem., 1995, 60, 4002

0

\ a V-bhBr OMe

I

/

N’ I

Bu$nH , AIBN , PhH reflux ,8h (syringe pump, 7h) *

~;~;NHco2Mx;:~ 2

co$k 30%

Lee.;

Whang,I-IS.; Chung,C.K. Tetrahedron

Mt.,

1995, 36, 913

360/ 0

co2M

Section 8 1

Amides from Amides

-L

(BnNEt&MoQ

107

, CHg12

82%

)

Ph

-78OC * rt ,30 min me2 Ilankumaran, P.; Ramesha, A.R.; Chandrasekaran. S, Tetrahedron L&t.,

me2

1995,

36, 8311

1.2.2 eq.BuLi , THF , -78OC+ 0°C 0 2.

0

Ph

N’

\

\ I d

NHMe 4

I

3. H30+ 4. Me$iCl , NaI , MeCN

/

WY. Pts, Tetrahedron

Lett., 1995,

/

Me

Ph

A

Ph 75%x92%

36,493

2 SnC12,2KI CH2C12 , rt , 12h N-(f6Hll

53% + 10%benzophenone Qmoka

T,; Iwama, T. Tetrahedron

Lett., 1995,

36, 5559

HC=CCH2Br,DMWDMF , NaH LiBr , O°C + rt THPO Liu, H.; Ko, S.-B.; Josien,H.; Curran.D.P, Tetrahedron

Lett., 1995,

36, 8917

Ph

Ph Ph

Mn(OAc), AcOH

D’Annibale,A.; Resta,S.; Trogolo,C. Tetrahedron

Lett., 1995,

36, 9039

87%

108

Compendium

42


Section 82

2% Rh#SMEPY)4 0

cwkt

N -b

Y Doyle. M.P,; Kalinin,

0

70% (96% ee)

cm2

A.V. Synlett, 1995, 1075 SPh

MeS

&SPh

neat, rt Id Ar = 4-methoxyphenyl

66%

Ar . x; Nakaharu, T.; Nishimura, M.; Nishikawa, A.; Kameoka, C.; Ikeda, M. Tetrahedron, m. . 1995, 51, 2929 Ph Bu$nH, Ph

I \

AIBN

Ph

*

+

toluenhe , reflux

Me bile

Me

47% 12% Sato, T.; Chono, N.; Ishibashi, H.; Ikeda. M, J. Chem. Sot., Perkin Trans. I., 1995, 1115

@O ,SO2Tol

Ph

Ph

Me$GCHC02Et

41%

N -7

-

. u-. UJt;

SECTION

b/ TolO# Arora, A. J. Chem. Sot., Perkin Trans. I., 1995, 2605

82: AMIDES

FROM

AMINES

NaB03a4 Hfi

P L -N-Ph Nongkunsam,

C02Me

, CF3C02H

80°C

P.; Ramsden. CA, Tetrahedron

+

H

Lett., 1993, 34, 6773

B

N \

/

Ph 51%

Ph

Section 82

Amides from Amines

109

0

NHBn

Sn[NUMS)212 9hexme 9fi CO2Me

C3H

pivalic acid

A

5r

C3H7

N\

P

Bn

89% Wang, W.-B.; w

J. Am. Chem. Sot., 1993, 115, 9417 NCCH2CH0,

c8H

17-NH2

Duetsch, J.; Niclas. H.-J,Synth.

r-t, 6h

) C&I 17-NHCH0 Commun., 1993, 23, 1561

78%

1. N-cyclohexyl-N’,N’,N”,N”tetramethylguanidine , pyridine toluene , CO2 , - 10°C 2. toluene , SOCl;! , -1OOC 77% McGhee. W.D.; Pan, Y.; Talley, J.J. Tetrahedron

1. 2eq.

Let?., 1994, 35, 835

R pkPhP Cl

3eqNEt3,THF

67%

-

2. excess NaH Osbom, H.M.I.; Cantrill, A.A.; Sweenev. J.B.; Howson, W. Tetrahedron

Let?., 1994, 35, 3159

xylene , 150°C, 3h NHBn -Gee.

c), N I Bn

0 93%

DLL; Ramaseshan, M. Synlett, 1994, 743

oc

NHBn

CO, MeCN Pd(PPh3)4, NBu3

OTf

Qiso. G.T,; Meyer, A.G. Tetrahedron,

quant. 1995, 51, 5585

110


C3H7wmt*

co 9w@w2

9dPPP )

Section 83

C3~7Aqqmt2 0

b&&&.

. S.-L; Imada, Y.; Nishimura, K. Tetrahedron,

SECTION

83: AMIDES

FROM

78%

1994, 50, 453

ESTERS ,0C02t-B u

H-N moAc

\

OCOzt-Bu

C02t-Bu

I

K2CO3, IT, Id

mNxC02t-Bu

77% . J-P,; Thorimbert,

S.; Touzin, A-M. Tetrahedron

L&t., 1993, 34, 1159

h

2 eq.Sn[NTMS2]2 2 eq.Me2NCH2CMe20H Ph-CO2Me

*

2 eq.PhCHMeNH2

dyA H

Wang,W.-B.; Restituyo, J.A.; Roskamo. E.J, Tetrahedron

Ph LA

0

1.5SnFJ(TMS)& , THF

0 OMe

97%

L&t., 1993, 34, 7217

*

1.5Et2NHaHCl,rt , 18h

Ph 3

mt2

52% Smith, L.A.; Wang, W.-B.; Burnell-Curty, C.; Roskamn.E.J, Synlett, 1993, 850 0

iPrNH2, t-BuOH ,1.5d 0-

Chen.S.-T; Chen,S.-Y.; Chen,S.-J. Tetrahedron 0 C3H

7A

*

25OC

I H

NaEtzAl(Bn)z, toluene OEt

reflux , lh

69%

Lett., 1994, 35, 3583

0 * C3H

72

NHBn 93%

Sim, T.B.; Yoon. N.M,SynZett,

1994, 827

Section 85

/ PMP

Amides Tom Halides

r

Ph

I N

)

111

(Lp+

]

(;p

2. NEt3 , CH2C12

PMP = 4-methoxyphenyl

. 30) 99% (70 Annunziata. R,; Benaglia, M.; Cinquini, M.; Cozzi, F.; Ponzini, F.; Rimondi, L. Tetrahedron, 1994, 50, 2939

0 A

1. BC13-SMe2 SPY

Ph/\i

p-l =-

Me

Ph

NMe2

74% (78%ee)

*

2. O*\

ph3N-PMP

PMP

PMP = N-4methoxyphenyl Annunziata,R.; Benaglia,M.; Cinauini.M.: Cozzi. F, Tetrahedron Lett., 1995, 36, 613

SECTION

84:

AMIDES FROM THIOETHERS

ETHERS,

EPOXIDES

AND

NO ADDITIONAL EXAMPLE!3

SECTION

85: AMIDES Br SiMe3

FROM

HALIDES

1.Mg

AND SULFONATES

m

2. PhNCO

83%

Co& Jr.. M.P,; Pollock, C.M. J. Org. Chem., 1993, 58,

-MgBr

c1’NMe2

+ bme2

cat. NiClz(dppe), THF vrt Babudri,F.; Fiandanese, V.; Marchese.G,; Punzi, A. Synlett,

1994,

719

90%

112


Section 87

1. CS2, THF PhMgBr

2. BtS02CF3

63%

w

3. BuNI&

. ~A.R.;

SECTION

Bt = benzotriazol-l-y1 Moutou, J.-L.; Yang, 2. Synlett, 1995, 99

86: AMIDES

FROM

NHBu

HYDRIDES


SECTION

87: AMIDES

FROM

Me02C-

aldehydes canalsobe used

KETONES

NH2

TEA, N~BH(OAC)~ DCE , rt ,45h

t

00-b 92%

bdel-Manid. A.F,; Harris,B.D.; Maryanoff, C.A. Synlett, 1994,81 OTIPS

1. 10eq.TMSN3 2 eq.PPTS CH2C12,rt ,2d 2. UV , 0°C , lh 79~89%

Evans. P.A%;Modi, D.P. J. Org. Chem., 1995, 60, 6662

Milligan, G.L.; Mossman,C.J.; Aube, J. J. Am. Chem. Sot., 1995, 117, 10449

1. NI$OSO3H, SiO2 2. Hz0 , microwave Laurent,A.; Jacquault,I?; Di Martino, J.-L.; Hamelin.J, J. Chem. Sot. Chem. Commun., 1995, 1101

Section 89

Amides from Alkenes

SECTION

88: AMIDES

FROM

113

NITRILES

UHP , cat. K2CO3 , aq. acetone N

PhCN

P

rt, lh

UHP = urea-hydrogen peroxide adduct Balicki. R,; Kaczmarek, L. Synth. Commun., 1993, 23, 3149 H

L

H

Mn02, SiO2, hexane

CN P Breuilles,P.; Leclerc,R.; m.

rt,lod

*

D, Tetrahedron

92%

Pu

Lett., 1994,

NH2

35,

1401 0

Al203 (neutral), 60°C, Id

70%

CN

t * w NH2 Wilgus,C.P.; Downing,S.; Militor, E.; Bains,S.; Pagni. R&k: Kabalka. GW, Tetrahedron Lett., 1995, 36, 3469

SECTION

89: AMIDES

FROM

ALKENES

TsN=IPh, Mn salencatalyst * PhA Ph pyridineN-oxide, MeCN , rt Noda, K.; Hosoya,N.; Irie, R.; Ito, Y.; Katsuki. T, Synktt, 1993, 469 1. PhI=NTs, Cu(OTf)2, MeCN e 2.0.1 M NaOH

Ts\

34%

N-Ts

N d-

77%

JCL; Muldowney, M.P. Synlett, 1995,949

SECTION

90:

AMIDES

FROM

MISCELLANEOUS

COMPOUNDS

BnN=C=O, hv (Pyrex filter) @

\

42% cr(m3

v. J.H.; Ahmed,G.; Ferguson,M.D. Tetrahedron

L&t., 1993,34, 5397

114

Section 90


o=

Bu&Re04,

N-OH

CF$03H,

MeNO

*

50% H2NOHaHCl

Narasaka, K.; Kusama, H.; Yamashita, Y.; Sato, H. Chem. Lett., 1993, 489

)iic,

T”Sy

v

+ a

2STMSOTf,CH; 7

202

n=

aux

,O,

Ph

Ph

Pouilhes,A.; Langlois.Y,; NshimyumuKiza, P.; Mbiya, K.; w.

30% (>95:5enbexo) 1,. Bull. Sot. Chim. Fr.,

1993, 130, 304

9\ //O

0\//

2. 1. MeMgCl BEt3 *

Ph’\

3. H2NOS03H Me Huane..-C,; Reinhard,E.J.; Reitz, D.B. Tetrahedron

0 50%

PhHs \ NH2

Mt., 1994, 35, 7201

hv , hexane, PhNMe2

ipmaJ( = 0.77 Post,A.J.; Nwaukwa,S.; Morrison. H, J. Am. Chem. Sot., 1994, 116, 6439

CO, MeOH, Pd(dpppK129PhH K2C03,160°C

NHCOzMe 59%

MeO$HN02N

Reddy,N.P.; Masdeu,A.M.; El Ali, B.; Alner. H, J. Chem. Sot. Chem. Commun., 1994, 863

Section 90A

Protection of Amides

Ph. 70 \

Mn(tpp)Cl

, MeCN

3o”c

0

115

Ph.

* P

0 60% tPP = tetraphenylporphyrin Suds. K,; Sashima, M.; Izutsu, M.; Hino, F. .I. Chem. Sot. Chem. Commun., 1994, 949 Montmorillonite

N-OH

K-10, microwave *

NHPh

7 min

Bosch, A.I.; de la Cruz, P.; Diez-Barra,

(17% with heating and no microwave) E.; Loupy, A.; Langa. F, Synlett, 1995, 1259

DMF , POC13, 90°C ,.

N-OH Majo, V.J.; Venugopal,

CHO

0 M.; Prince, A.A.M.;

N-OH

60% Perumal. P.T, Synth. Commun., 1995, 25, 3863 H N

0.2 Bu$lRe04,0.2 CF$OsH MeNO*, reflux ,0.5 NH~OH~HCl

Phx>”

0

CJ Ph Kusama, H.; Yamashita, Y.; Narasaka, K. BuZl. Chem. Sot. J’n., 1995, 68, 373

SECTION

*

90A:

PROTECTION

91%

OF AMIDES

0

0 0

2 Mn(OAc)3.2 H20, EtOH CU(OAC)~~H~O, 55OC 45%

N4

N4 \

SiMe3

OH Ghosh, A.; MiI&r. MuI Tetrahedron

L&t., 1993, 34, 83

\

H

SiMe3

116

Compendium


Section 90A

1. AlC13 ,6O”C 2. PhOMe ,6h

Kim, J.N.; Ryu. E.K, Tetrahedron

Mg(ClO&

Boc P Stafford.=; 7873

Lett., 1993, 34, 3567

99% 50°C ,20h * PA NHMe r’ Me Brackeen, M.F.; Karanewsky, D.S.; Valvano, N.L. Tetrahedron L&t., 1993, 34,

Mg(OMeh P

0

, MeCN

, MeOH

0

CO$-Bu Wei, Z.-Y.; Knaus.J Tetrahedron

P -

0 +

H

90%

Lett., 1994, 35, 545 5 eq. Ac20,4% 2.2 eq. Bu$nH

Pd(PPh& , CH2C12

NHOMe AcHN * G 58% o Roos, E.C.; BernaM, P.; Hiemstra, H.: Speckamp. W-N,; Kaptein, B.; Boesten, W.H.J. .I. Org. Chem., 1995, 60, 1733 rt , 10 min


Amines from Alcohols

Section 93

CHAPTER

7

PREPARATION

SECTION

91: AMINES

OF AMINES

FROM

ALKYNES

NO ADDITIONAL

SECTION

92: AMINES

\ox

SECTION

I

117

93: AMINES

FROM

ACID DERIVATIVES

NO ADDITIONAL

FROM 1. MeLi,

EXAMPLES

EXAMPLES

ALCOHOLS

AND THIOLS

THF

2. PhCN , warm OH Fitzgerald, J.J.; Michael, F.E.; Qlofson. R.A. Tetrahedron

(J-JPh

*

47%

/

L&t., 1994, 35, 9191 Me

1. BuN3, 2.5 eq. TfOH 95% 2. NaBH4 mn.

W.R,

Bu

Fang, W. J, Org. Chem., 1995, 60,496O PhCH2NHTf

, DEAD,

PPh3

PhCHzOH 93% Bell, K.E.; Knight. D.W; Gravestock, M.B. Tetrahedron

==c OH

Lett., 1995, 36, 8681

HNBn2, SnC12, NE@, THF ,2d

w NBn2

2% Pd(PPh3)4, 50°C

70% Masuvama.

Y.; Kagawa, M.; Kurusu, Y. Chem. L&t., 1995,

1121


118

SECTION

94: AMINES Me3S’

PhCHO

FROM

ALDEHYDES

-3

Me3SiCl ,29h

Jahn, U.; Schroth. W, Tetrahedron

(t

Section 94

Lett., 1993,

34, 5863

1. C$I 1lCHO , BER , EtOH NH2

Et3NHCl 2. BER , NaOH

* o-

NHCH2C5H1 l

BER = borohydride exchange resin Yoon. N.M.; Kim, E.G.; Son, H.S.; Choi, J. Synth. Commun., 1993, 23, 1595 LiAl(NHBn)d,

89%

ether

25OC, 7h Solladie-Cavallo.

A,; Bencheqroun,

M.; Bonne, F. Synth. Commun., 1993,

23,

1683

1. Bzt-SNH2 , NaOH , EtOH 2. PhSN(TMQ, cat. TBAF , THF Ph

3. Bu$nH

-?B&in,

, cat. AIBN , cyclohexane

CHO

61x69%

J.; Fouquet, E.; Zard. SZ, Tetrahedron,

1994, 50, 1745

1. Me2NH*HCl, Ti(OiPr), EtOH ,25OC, 10h

, NEt3 *

ph-CHO 2. NaBH4,25OC Bhattacharvva,

PhCHO

S, .I. Org. Chem., 1995,

Phw

NMe2

, 10h

95%

60,4928

1. BnNH2, PyeBH3, MeOH MS 481,16h

>

Ph/\N-Ph

2.6NHCl 3.8 N NaOH Bomann, M.D.; Guch, I.C.; DiMare. M, J. Org. Chem., 1995, 60, 5995 TsNH2, Si(OEt), , 160°C, 6h > PhCHO Love. BE; Raje, P.S.; Williams II, T.C. Synlett, 1994, 493

PhCH=NTs

I H

87%

68%

Section 96

119

Amines from Amides

BnNH2 , Bentonite , rt ,3h

PhCHO

w

80%

PhCH=N-Bn

ketones can also be used Saoudi, A.; Benguedach, A.; Benhaoua. H, Synth. Commun., 1995,25,2349 Related Methods: Section 102 (Amines from Ketones)

SECTION

95:

AMINES ARYLS

FROM

ALKYLS,

METHYLENES

AND


SECTION

96: AMINES

FROM

AMIDES

C6Hl3

Fisher, G.B.; Fuller, J.C.; Harrison, J.; Goralski, C.T.; Sin Tetrahedron Lett., 1993, 34, 1091

R,

KH , THF , Cp2ZrHC1

JyClOH21 t

PhJL

-2OOC + rt

PlrJ

NwoH21

86%

Schedler, D.J.A.; Godfrey, A.G.; Ganem, B, Tetrahedron Lett., 1993, 34, 5035 1. LiHMDS ; BnBr 2. LiHMDS ; Me1 3. LiA1H4 4. H2, Pd-C

G? Ph 0 Westrum, L.J.; Meyers. A& Tetrahedron

+ H’ 89%

Lett., 1994, 35, 973

Ph Tic13 ,3 eq. CsK Ph

Fs

90% H A; Hupperts, A.; Ptock, A.; Janssen, E. J. Org. Chem., 1995, 60, 5215

H

120

Section 97


0

A

HBr ,163OC

*

N

H-Nw-ph

NI-IPheHBr

L-l

88% Poindexter. Cr.&; Bruce, M.A.; LeBoulluec, K.L.; Monkovic, I. Tetrahedron L&t., 7331 /sWF3

1994,

35,

t-BuLi , THF , -60°C, 3h t-Bu

52% Bozee-Ogor, S.; SaIou-Guiziou, V.; Yaouanc, J.J.; Handel. H, Tetrahedron L&t., 1995, 36, 6063 Ph 3 Ti (powder), THF, 21h 3 TMSCl , reflux

t

Ph

AN-(

Ph

I

H r. pL; Hupperts, A. J. Am. Chem. Sot.,

1995,

117,

4468

H I

N

S

30%H202, AcOH, 25OC w

Me Grivas, S.; Ronne, E. Acta Chem. Scand. B.,

1995,

49,

H n-

N \

Me

85%

225

Related Methods: Section 105A (Protection of Amines)

SECTION

97: AMINES

c

N -Ph

AImena, J.; Foubelo, F.; m

FROM

AMINES

1.5 Li (powder) , TI-IF cat. CteHs , -78OC, 6h 2.H20 M, Tetrahedron

* vNHPh 93%

Lett., 1993, 34, 1649

Section 97

Amines from Amines

PhCHO , TFA

Me \ H

121

Et$iH , CH2C12, O°C

83%

\ H

Appleton, J.E.; Dack, K.N.; Green, A.D.; Steele. J, Tetrahedron

L&t., 1993, 34, 1529

9-BBN , THF ,20h *

Wy-”

56%

H ‘Ar Ar = 3,4-dimethoxyphenyl Gaul, M.D.; Fowler, K.W.; Grieco. P.A, Tetrahedron L&t., 1993, 34, 3099

70%

2. H30+ Maye, J.P.; Nerrishi. E. Tetrahedron

L&t., 1993, 34, 3359

?h

Ph

\ I/ 0 h

A

T

A 10 eq. MeLi, PhH ,5O”C w-

I v H’

I v

+

I-Y

N

NH2

Y >60% Genin, M.J.; Biles, C.; Romero&D.L, Tetrahedron

0

Mt.,

20% 1993, 34, 4301

1. s-BuLi , TMEDA 2. Me1

3. s-BuLi, TMEDA * Mz&’cx N 4. Me1 I Boc I&&. P,; Lee, WK. J. Org. Chem., 1993, 58, 1109

62x41% N

I Boc

Me

122

Compendium

9


Section 97

t-Bu 1.1.5 LDA, THF , O°C 62%

THF, 15h , O°C + rt 3.3 eq. K2CO3, MeOH heat, 3h N.G,; Keppens, M.A.; Stevens, C.V. Tetrahedron

Lett., 1993, 34,4693

2.5 eq. LiBHEt3 , THF , rt 84% (1:l cixtrans) Blough, B.E.; Carroll, F.I. Tetrahedron

0

N

I H Kanth, J.V.B.; Pemv.

\aI/

NH2

H L&t., 1993, 34, 7239

2.PhBr,THF,rt,6h l.Li,THF 3. MeOH ; 20% HCl MJ.

)

-

0

86%

N I Ph

Org. Chem., 1993, 58, 3156 H I

5% Pd(OAc)2, 5% PPh3 100°C ,3.5d, Na2CO3 +65, ’ * Larock. R.C,; Berrios-Pefia, N.G.; Fried, C.A.; Yum, E.K.; Tu, C.; Leong,W. J. Org. Chem., 1993, 58, 4509 I

ONMe

1. w&r
95% 36, 7357

Section 105A

CL

Protection of Amines

139

, DCE , reflux

N Me 2. MeOH, reflux I Bn Yane. B.V,; O’Rourke, D.; Li, J. Synlett, 1993, 195

*

TiC13-Li , THF , reflux ,22h Me2NBn c, Talukdar, S.; Banerji. A, Synth. Commun., 1995, 25, 813

(R

74% N I H

Me2NH

Me

55%


140

Section 107


CHAPTER

8

PREPARATION

3

SECTION

OF ESTERS

106: ESTERS FROM ALKYNES OH

xylenes , 150°C

H OEt

~ 72%

OH Liang, L.; Ramaseshan, M.; MaGee. D.1, Tetrahedron,

SECTION

0

0

1993, 49, 2159

107: ESTERS FROM ACID DERIVATIVES

The following 1. 2. 3.

2x

types of reactions are found in this section:

Esters from the reaction of alcohols with carboxylic acids, acid halides and anhydrides. Lactones from hydroxy acids Esters from carboxylic acids and halides, sulfoxides and miscellaneous compounds 0 0

tiI

0 Li [Binol-AlHOEt] -78OC +

, THF rt -

0 Matsukl.;.

(84% e-e)

Inoue, H.; Takeda, M. Tetrahedron CO2I-r

0

I ti

Lett., 1993, 34, 1167

PhCHzOH ,2,6-lutidine C

k/ Cl 00S\fN

Cl

\

Folmer, J.J.; Weinreb. SM, Tetrahedron

9 C&C12

-78OC + rt Lett., 1993, 34, 2737

C02CH2Ph

81%

69%

Section

Esters from Acids

107

K

141

2

H

Si( iPr),

a

90°C

OH Soderauist, J.pL; Miranda, E.I. Tetrahedron Lett., /

0-S 1993,34,4905

/

C02H

TEOA = triethyl orthoacetate Trujillo, J.I.; Goaalan.AS, Tetrahedron Lett., 1993,

i(iPr)3

93%

C02Et

7355

34,

C&Il@H , TsOH, neat PhC02H

my.

PhC02C8H17 97% microwave,3 min A,; Petit, A.; Ramdani,M.; Yvanaeff,C.; Majoub,M.; Labiad,B.; Villemin. D, Can. J.

Chem., 1993, 71, 90

Ph-CO

1. NBS CH$I;!, MS 481 O°C, PPh3

2H

2. PhCH20H, Py , lh Sucheta,K.; Reddy,G.S.R.;Ravi, D.; -Q&W.

fd

Ph

phwco2H

~

VPh

Ph 7

x Tetrahedron

98%

0 Lett., 1994, 35, 4415

20%Tic14+ 2 AgC104 Ph+P (ArCO)20 9MS3A Ar = 3,5-trifluoromethylphenyl Shiina,I.; Miyoshi, So.; Miyashita, M.; Mukaiyama,T. Chem. Lett.,

HOqCHz)lo

JL OH

Ph

0 OH

5%TiCLz(OTf)z, (ArCO)20 3 TMSCl , CH2C12 (2 mM) reflux (slowadditionover 5 h)

Ar = 4-trifluoromethylphenyl Shiina, I.; Mukaiyama,T. Chem. Lett., 1994, 677

*

0

90% 1994,

515

A==

0

CJ32ho

83% + 10%diolide

142


C17H31C~H

*

cat. DMAP , lh

Section 108

C1f131C%cH~H=CH2

85% Akiyama, A.; Konda,Y.; Takayanagi,H.; Harigaya,Y. Tetrahedron Mt., 199% 36,

NK.; 113

Togo. H,; Muraki, T.; Yokovama.M, Tetrahedron

Lett., 1995, 36, 7089

Bu-C=C-H, 100°C,5 eq.NEt3 5% Pd(PPh&t, ZnCl;! 84% Liao, H.-Y.; Chew. E.H, J. Org. Chem., 1995, 60, 3711 Furtherexamplesof thereactionRC02H + R’OH + RC02R’areincludedin Section108(Estersfrom AlcoholsandPhenols)andin Section30A (Protection of CarboxylicAcids).

SECTION

108: ESTERS

FROM

ALCOHOLS

AND THIOLS

Furtherexamplesof thereactionROH + RCO2R’areincludedin Section107 (Estersfrom Acid Derivatives)andin Section45A (Protectionof Alcoholsand Phenols). 1. BuLi, THF, rt PhmOH

;s ph/n/Yco2Et . C02Et 5% Pd(PPh3)4,8h (80:20 E.-Z) 10%PPh3,reflux Star$, I,; Star& I.G.; IWovsky, P. Tetrahedron Lett., 1993, 34, 179

80%

Section 108

143

Esters from Alcohols

OH

&&j)oa.

CL;

3.5 Ca(OC1)2,2

C02Me

AcOH

89%

32MeOH,darkJd MeCN , rt Nice, L.E.; Shaw, A.W.; Nestor, N.B. Tetrahedron

Lett., 1993, 34, 2741

1. sOC12, DMF

4 C 13H27CH20CH0 2. H20 I.; Garcia, B.; MuAoz, S.; Pedro. J.R,; de la Salud, R. Synlett, 1993, 489

CL3H2$H20H Femtidez, tioH

KNOflFyl.25

Hz0

CH2C12,O”C

+ rt

-

95%

-ON02 95%

Olah. G.A,; Wang, Q.; Li, X.; P&ash,

G.K.S. Synthesis, 1993, 207

1. Cr(CO)9THF,

THF, 55OC t

w. 81%

m.

P,; Rahman, S.; Ward, E.L.M. Tetrahedron

Lett., 1994, 35, 3801

Pb(OAc), , PhH , CO C3H77

OH

Tsunoi, S .; Byu. I.: Son& Hok

m

40°C) Id

N, .I. Am. Chem. Sot., 1994, 116, 5473 NaBrO2, Al203 9 c&cl2

57%

.

T,; Hirano, M.; Iwasaki, K.; Ishikawa, T. Chem. Z&t., 1994, 53

30:1 (2,3-antixyn)

Panek.J.S,; Garbaccio,R.M.; Jain,N.F. Tetrahedron

BuOH ,0.2 M CAN reflux ,75 min

-

t

Lett., 1994, 35, 6453

OH Iranpoor.N,; Mothaghineghad, E. Tetrahedron, 1994, 50, 1859

158

Compendium of Organic Synthetic Methods, Vol. 9

Section 124

OMe

&rk.R.M.;

Gac, T.S.; Roof, M.T.S. Tetrahedron Lett., SPDBTO

\

1994,

35, 8111

SPDBTO 1. Hg(OAc);! , CH2C12 rt , 18h ) Y + +* 2. aq. NaCl 3. Bu$nH, THF

SPDBTO

# n\/O

OH

+ x

\/O

.

1) 93% Garavelas, A.; Mavropoulos, I.; Perlmutter.P.; Westman, G. Tetrnhedron Lett., 1995, 36,463

(7

v

5% Pd(OAc)2, DMSO ,02 23OC, Id OH

H‘*

*

623

Ronn, M.; BackvaIl, J.-E.; Andersson. P.G, Tetrahedron Lett.,

OH

1995,

BnBr , Cs2CO3, MeCN

OH

92%

OBn

80°C Lee. J.C.; Yuk, J.Y.; Cho, S.H. Synth. Commun.,

90%

,+ H 0 36, 7749

25, 1367

1995,

1. A@ 2. (Cp)zTiMez

OiPr 80x80%

3. H2, Pd/C Billington, D.C.; Dorey, G. Synth. Commun., 1995,

SECTION

124: CHO

CsHlJ

ETHERS, EPOXIDES FROM ALDEHYDES

25,

1633

AND THIOETHERS

BuOH , Pd/C , H2 (40 bar), 100°C

also works with ketones Bethmont, V.; Fache, F.; J,eMaire. M, Tetrahedron Lett.,

w

1995,

c8H13 36,4235

,OBu

95%

Section 128

Ethers from Esters

Me&O-

*

PhCHO Et$iH -s.; 4367

159

, TMSOTf

, CHzC12, -3OOC +

O°C

Mori, H.; Kitano, K.; Yamada, H.; Nishizwa.

(t

Ph-Ow

M, Tetrahedron

CH2N2

CHO

A~(OAI-)~ , -78OC , lh

Maruoka, K.; Conception,

Ar = 2,5diphenylphenyl A.B .; Yamamoto. H, Synlett, 1994, 521

ONTs I Ar’sN Me

83%

,NaH,THF

0 H ‘h,, -5OC, Id PhA Baird, C.P.; Taylor. P.C, J. Chem. Sot. Chem. Comnun., 1995, 893 PhCHO

SECTION

125:

126:

ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLS

ETHERS, EPOXIDES FROM AMIDES NO ADDITIONAL

SECTION

127:

ETHERS, EPOXIDES FROM AMINES NO ADDITIONAL

SECTION

128:

ETHERS, EPOXIDES FROM ESTERS 1. Dibal , -78OC

Ph’dco2Me

63% (70% ee)

t

NO ADDITIONAL

SECTION

99% L&t., 1994, 35,

2 . TMSOTf

9Py

Kiyooka. S,; Shirouchi, M.; Kaneko, Y. Tetrahedron

EXAMPLES

AND THIOETHERS EXAMPLES

AND THIOETHERS EXAMPLES

AND THIOETHERS OSiMe3 p

Ph T

OMe Lett., 1993, 34, 1491

91%

160


Section 129

1.2SmI2, -3OOC + l-t Ph

2. A@,

J

Mobder.

DMAP , TEA CH2C12

G.A; McKie, J.A. J. Am. Chem. Sot.,

115, 5821

PhSH, Pd2(dba)3 , dppb ) THF, Id

mocqMe

Goux, C.; Lhoste,P.; Sinou.D, Tetrahedron,

SECTION

1993,

ETHERS, ETHERS,

129:

1994,

EPOXIDES EPOXIDES

AND THIOETHERS AND THIOETHERS

OBn

\a /

ow

2. H30+

Ph

44

S \

Ph

0 Satoh.T.: Horiguchi,K. Tetrahedron OMe

Lett., 1995, 36, 4429

1.2.5 t-BuLi , THF -loo”c

t

2. EtCHO Lett., 1995,

-OH

36, 8235

NaBHgN, Bu3SnCl, AIBN 9h

oc

90% 0

* (x

66%

1994,38,2165

1. e’ , Ni (cyclam), DMF , 20°C Mg anode,C fiber cathode

Me,y A

p-Tel.

d?

I

Olivero, S.; CIinet, J.C.; Dufiach,E. Tetrahedron

FROM

OBn

0

Itoh, A.; Hirose,Y.; Kashiwagi,H.; &&&i. Y, Heterocycles,

I

83%

50, 10321

2 BF3*OEt2,CH2C12 / 0ch

mSPh

12H25

Srikrishna.A,; Viswajanani,R. Synlett, 1995, 95

(t

80%

W2H25

62%

Ethers from Ketones

Section 132

161

Phi ,2% Pd(OAc), ,3 NEt3 6% PPh:, , DMF , 70°C

Hillers, S.; J&ger. 0, Synlett, 1995, 153

SECTION

130:

ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATES

BER-PhSSPh , MeOH, reflux * CsI-I17-S-Ph Yoon. N.M.; Choi, J.; Ahn, J.H. J. Org. Chem., 1994, 59, 3490 c&3

17Br

\ 0I

96%

MeSCHzCl, AlC13 CH2C12 , O°C

/

Olah. G.A.; Wang, Q.; Neyer, G. Synthesis, 1994, 276 PhSH, rt SPh Lee, S.B.; Hong,J.-I, Tetrahedron

tett., 1995, 36, 8439

RelatedMethods:Section123(EthersfromAlcohols).

SECTION

131:

ETHERS, EPOXIDES FROM HYDRIDES

AND THIOETHERS

PIFA = phenyliodine(III)bis(t.rifluoroacetate) Kita. Y,; Takada,T.; Mihara, S.; Tohma,H. Synlett, 1995, 211

SECTION

132:

ETHERS, EPOXIDES FROM KETONES

Tsai. Y-M,; Tang,K-H.; Jiaang,W-T. Tetrahedron

AND THIOETHERS

Lett., 1993, 34, 1303

88%

162


PA,,

TBAF

Capperucci,A.; moceai. A. Tetrahedron

Section 134

A; Ferrara,M.C.; Bonini, B.F.; Mazzanti, G.; Zanti, P.; Ricci,

Lett., 1994, 35, 161 0

/oAc,

Rh2(Ok)4

*

PhF , 10h b

Pirrun~.M.C,; Lee,Y.R. Tetrahedron

0

69%

Lett., 1994, 35, 6231

RelatedMethods:Section124(Epoxidesfrom Aldehydes).

SECTION

133:

ETHERS, EPOXIDES FROM NITRILES

AND THIOETHERS


SECTION

134:

ETHERS, EPOXIDES FROM ALKENES Asymmetric

AND THIOETHERS

Epoxidation

-00

Ph \ -c

/N-O

, NaOCl +

Mn-salenderivative O°C , pH 11.3

&

58% (77% ee)

Chang,S.; Lee, N.H.; bobsen. m

J. Org. Chem., 1993, 58, 69 39

Mn (salen)catalyst , lh 1%H202, O°C, CH2C12 Schwenkreis, T.; Berkessel,A, Tetrahedron Lett., 1993, 34, 4785

CO2Et

Section 134

Ethers from Alkenes

threitol-strapped iodosylbenzene

Mn-porphyrin

163

, CH$I;!

t

A0

Ph-

, 1,Sdicyclohexylimidazole

86% (69% ee, R+) J.P,; Lee, V.J.; Zhang, X.; Ibers, J.A.; Brauman, J.1 J, Am. Chem. Sot., 1993, 115,

Collman. 3834

l

chloroperoxidase H202

,Bu

, acetone

Bu

9pH 5

----+v

0

78% (96% e-e, 2R3S) Allain, E.J.; Hager, L.P.; Deng, L.; Jacobsen, E.N. J. Am. Chem. Sot., 1993, 115, 4415 Me02%,, Ph Me02C

I

s

Ph

,B-OMe

0 0

t-BuOOH Manoury, E.; Mouloud,

H.A.H.; Balavoine, G.G.A, Tetrahedron

35% (22% ee , S,S) Asymmetry, 1993, 4, 2339

Mn salen catalyst, 02 PhH,rt

51% (52% ee) T.; Yamada, T.; Nagata, T.; Imagawa, IS. Chem. Lett., 1993,327

Mukaiyama,

-0 Ph )=/ Ph

Ph 32 \

0 Ph

/N-o

* cat. Mn salen, O°C , buffered bleach , pH 11.3

)\7/ Ph

0

69% (93% ee, S,S) Brandes, B.D.; &obss

J. Org. Chem., 1994, 59,4378 cat. Mn(salen) , CH2C12 -

phN

,,yp (42%ee, lS,2S)

Pietikainen.

P, Tetrahedron

Lett., 1994, 35, 941

49%

164


\m I/

Section 134

\ I/ 02

Mn salen catalyst, PhIO , O°C

0

72%(98%ee)

Sasaki,H.; Irie, R.; w.

T, Synlett, 1994, 356 2 PhIO, Mn salencatalyst

ph-

t

Ph

Sasaki,H.;Irie, R.; Hamada,T.; Suzuki,K.; mki. Mn salencatalyst, t-BuCHO PhA

“TPh

rt T, Tetrahedron,

27%(15%ee, lR2R) 1994, 50, 11827

w

02,fl

28% (63:37 cis:trans) 80% eefor cis Nagata,T.; Imagawa,K.; Yamada,T.; Mukaiyama,T. Chem. Lett., 1994, 1259

02, Mn salencomplex, rt NM1 , pivaladehyde, PhF

78%(63%ee) T,; Imagawa,IS.; Nagata,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994, 67, 2248

B.

Mn (salen)catalyst, Bu4NIO4 imidazole, rt ,3h

Ph

53%(47%ee, lR,ZS (-) )

. . ..*

Pletlkamen.

Tetrahedron

c \

I

Lett., 1995, 36, 319

20%4-Ph-pyridineN-oxide, O°C 5%Mn salencomplex, CH2C12

/

Bran&s, B.D.; Jacobsen. E.N, Tetrahedron Lett., 1995, 36,5123

Section 134

Ethers from Alkenes

Ph-

165

8% Mn salen complex , mcpba , NM0

0

*

Ph4l

CH2C12, -78OC

89% (86% ee) Palucki, M.; McCormick, G.J.; Jacobsen. E.N, Tetrahedron

Lett., 1995, 36, 5457

chloroperoxidase , KOAc , Hz02 Ph

antifoamA, aq.acetone,pH 5.2 sodiumcitrate

*

Ph4

1111l111

0

89%(49%ee) Dexter, A.F.; Lakner,F.J.; Campbell,R.A.; Hager.L.P,J. Am. Chem. Sot., 1995, 117, 6412

a3 \

I

NT.;

02 , Mn salencatalyst, t-BuCHO

/

70%(64%ee) Imagawa,K.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1995, 68, 1455

Non-Asymmetric

Epoxidation

BIPA , FeCl2,02 70°C, Id

mo.

BIPA = N,N’-bis(2-(4-imidazoloyl)ethyl)-2,6-pyridinecarboxamide TJ Moriuchi, T.; Mikami, S.; Ikeda, I.; Ohshiro,Y. Tetrahedron Lett., 1993, 34, 1031 cat. [K-lO-montmorilloniteNi(acac)] 0

iBuCH0 , CH2C12,rt autoclave,10bar Bouhlel,E.; m. P,; Levart, M.; Montaufier, M-T.; Singh,G.P. Tetrahedron Lett., 1993, 34, 1123 -0. P,; Levart, M. Tetrahedron L&t., 1993, 34, 1127

ph*Ph

[CoCl&licylaldehyde-L-serinemethylester] w 02,MeCN,rt,25h

Punniyamurthy,T.; Bhatia,B.; j,qbal.J, Tetrahedron Lett., 1993, 34,4657

‘“TPh 64%

67%

166


h

Fecat.,02,iPrCHO,rt

R.W,; Reihs,S.; Hug, M. Tetrahedron

alfrank.

Section 134

* pgF+ e,

Lett., 1993,

34,

96%

Ph

6033

10%(NH&H4PV6W&4v6 H20 02, DCE,25OC, 4h 2 eq.iPrCH0 77% Hamamoto,M.; Nakayama,K.; Nishiyama,Y.; Ishii. Y, J. Org. Chem., 1993, 58, 6421

P

Co(mac)2,EtCH(OEt)z

C7Hl5

97%

02, MS481.,45OC

mat = 3-methyl-2,4-pentanedibne Mukaiyama,T.; Yorozu, M.; Yakai, T.; Yamada,T. Chem. Lett., 1993, 439

0I msha.

.

CUE,

0

CH3CH0, CH2C12

02,rt, 17h

0

79% S.-I,; Oda,Y.; Naota,T.; Komiya, N. J. Chem. Sot. Chem. Commun., 1993, 139 urea-H202complexfmaleic acid =

BUN

Bu,/f

71%

Astudillo, L.; GaIindo.A,; Gonzalez,A.G.; Mansilla,H. Heterocycles, 1993, 36, 1075 1. [Mn*‘*(TPP)(Cl)], CHs12 I . O-D.;

0 2. imidazole, Bu@IO4,5h

Tangestaninejad, S. Tetrahedron Lett., 1994, 35,945

o= 0

, KHSO5 zc

+

H20KH2C12(pH 11) 18-crown-6,5”C w. .

(9 M,; Ito, S.; Tsutsumi,N.; M&&J,&

Tetrahedron

l

Mt.,

91) 80%

1994, 35, 1577

Section

167

Ethers from Alkenes

AgOAc/bipy/anode ACN (0.1 M LiCLO4) H20

Kandzia,C.; Steckhan. Tetrahedron

-%d

iPrCH0, Fe(AAEMA)3 p02

*

rt, 10h

(-)=, AAEMA =

87%

0

Mt., 1994, 35, 3695

00

Mastrorilli, P.; Nobile, C.F, Tetrahedron

Lett., 1994,

PhzP-‘-PPh, II

35, 4193 0

II

87%

* k=

Ph -LA,&;

0

0

F

Ph H202 Delair, P.; Blass,B.E. Tetrahedron Lett., 1994,35, 8123 S II

1.

EtOlPEt0

SBn

S

2. TBAF.3 H20 wG.;

82%

.

Mecichetti, S.; Neri, S.; Skowr0nska.A. Synlett, 1994, 267 NaOCl ,4-methylpyridine

hJ

P

w

PJ

88%

0

porphyrincatalyst/Mn ; Pereira,M.M.; Serra,AC.; Johns~&pe. R.A.W; Nunes,M.L.P.G. J. Chem. Sot., Perkin Trans. I., 1994, 2053

Y

YO~OZU. K;

Takai,

C7H

15

02 (1 atrn),2% Co(acac)z EtCH(OEt)2,45OC, 1Oh

> 48%

0 T.; Yamada,T.; Mukaiyama,T. Bull. Chem. Sot. Jpn., 1994,67, 2195


168

Section 134

Oxone, 0°C , Bu4NHS04 t

IOBn

acetone , CH-$&

OBn

, buffer 99%

Denmark.S.E,; Forbes,D.C.; Hays,D.S.; DePue,J.S.; Wilde, R.G. J. Org. Chem., 1391 M 0 ‘-x Fg 6

P

1995,

60,

, MeCN, O°C

> 15min Me Yang. DJ Wong, M.-K.; Yip, Y.-C. J. Org. Chem.,

1995,

60, 3887

CO2H \ I 2 US.;

0-J

hv , methyleneblue PhH , Hz0

/ \ Thanulingam,T.L.; Rajesh,C.S.; George,M.V. Tetrahedron

Chen,Y.; Beymond.J.-L, Tetrahedron Lett.,

1995,

Lett., 1995,

36, 1337

36,4015

t-B&OH, Ti(OiPr)d, SiO2 w rt, Id Fraile, J.M.; Garcia,J.I.; Mayoral. J,A,; deMhorval,

L.C.; Rachdi,F. J. Chem. Sot. Chem.

Commun., 1995,539

PhIO, NaOCl, Mn salencatalyst t Rasmussen, KG.; Thomsen,D.S.; mn. 2009

w.

92%

K.& J. Chem. Sot., Perkin Trans. l., 1995,

Section 135

Ethers from Misc.

t-B&OH,

169

OH

MeOH

CrS-2- molecular sieve

85%

. Joseph, R.; Sasidharan, M.; Kumar. R... Sud& . A... Ravmdmnathu Commun.,1995,134l

Formation

0

Bosman,C.; DA-ale.

of Other Ethers

PhSeSePh , CAN I

J. Chem. Sot. Chem.

MeOH ,30 min

-c,

A; Resta,S.; Troeolo. C, Tetrahedron

SePh 93% “%, OMe

Lett., 1994, 35, 6525

97%

Marshall. J.A,; Sehon,C.A. J. Org. Chem., 1995, 60, 5966 REVIEW:

“RationalDesignof Manganese-Salen EpoxidationCatalyts;PreliminaryResults,”Hosoya, IV.; Hatayama,A.; Irie, R.; Sasaki,H.; Katsuki.T, Tetrahedron, 1994, 50, 4311

SECTION

135:

ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS PhSSPh, SbC15,DCE OMe

w

PhS-(=)-OMe

reflux ,3h 76% Mukaiyama, T.; Suzuki, K. Chem. Lett., 1993, 1 LiAlH4, Tic14 PhSOzMe w 93% PhSMe Akgiin, E.; Mahmoud,K.; Mathis. C.% J. Chem. Sot. Chem. Commun., 1994, 761

170


\r’u S

[SiO2/SOCl2] 10min

-

‘rs\y

73%

Mohanazadeh. F,; Momeni, A.R.; Ranjbar,Y. Tetrahedron Lett., 0 II

Section 135

1994,

35,6127

CpzTiC12,Sm, THF , rt w

Ph/‘\Me Zhann. Y,; Yu, Y.; Bao, W. Synth. Commun., 0 II

Ph”‘\ Ph Wang, J.Q.; Zhanrr, Y.M,Synth.

1995,

77-88%

25, 1825

TiC14,Sm, THF , rt ,30 min Commun., 1995,

Ph/‘\Me

25, 3545

w

Ph”,

Ph


Section 138

CHAPTER

10

PREPARATION SULFONATES

SECTION 136:

171

Halides fkomAlcohols

OF HALIDES

AND

HALIDES AND SULFONATES FROM ALKYNES NO ADDITIONAL EXAMPLES

SECTION 137:

HALIDES AND SULFONATES FROM ACID DERIVATIVES PhIO , NBS , MeCN , 60°C *

Ph-C02H

Ph+Br 73%

Graven, A.; a

SECTION 138:

(96:6 cis:trans)

K& Dahl, S.; Stanczdc,A. J. Org. Chem., 1994, 59, 3543

HALIDES AND SULFONATES FROM ALCOHOLS AND THIOLS

PPh3, (C13COCh0 w PhCH2Cl PhCHzOH Rivero, I.A.; SomanatXlan.; Hellberg, L.H. Synth. Commun., 1993, 23, 7 11

1

95%

BBr~,CH$ld)°Cw < .

Pelletier, J.D.; poiu

Tetrahedron L&t., 1994, 35, 1051

TMSCl , DMSO wh7-4H

&y&

D.C, J. Org. Chem., 1995, 60, 2638

t

c$H 1741

95%

172

Compendiumof Organic Synthetic Methods, Vol. 9

o-

OH

12, pet ether, reflux , 1.5h

Section 142

42%

I

Joseph,R.; Pallan, P.S.; Sudalai, A.; bvindranathm. T, Tetrahedron Left., 1995, 36, 609 Me$iCl , BiC13 OH

rt ,90 min f Labrouihere, M.; Le Roux, C.; Oussaid,A.; Gaspard-Boughmane,H.; Dubu

quant. Bull. Sot.

Chim. Fr., 1995, 132, 522

REVIEWS:

“An Alternative Synthesisof Aryl and Heteroaryl Bromidesfrom Activated Hydroxy Compounds,” IQ&&&y. A.&; Li, J.; Stevens, C.V.; Ager, D.J. Org. Prep. Proceed. int., 1994, 26,439

SECTION 139:

HALIDES AND SULFONATES FROM ALDEHYDES NO ADDITIONAL EXAMPLES

SECTION 140:

HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLS

For the conversionR-H + R-Halogen,seeSection 146 (Halides from Hydrides). 2 eq. VO(OEt)CZ2,N2 MeCN , O°C+ rt Ph~si~3

*

PhwC1

6oo/ 0

Fujii, T.; Hirao. T,: Ohshiro. Y, Tetrahedron Lett., 1993, 34, 5601

SECTION 141: HALIDES AND SULFONATES FROM AMIDES NO ADDITIONAL EXAMPLES

SECTION 142: HALIDES AND SULFONATES FROM AMINES 1. TolSO~l 2. base PheNH2

3.NBS,THF,hv

Ph-

Br

86% Collazo. J&; Guziec Jr., F.S.; Hu, W.-X.; Pankayatselvan,R. Tetrahedron Lett., 1994, 35, 7911

Section 146

Halidesfrom Hydrides

173

SECTION 143: HALIDES AND SULFONATES FROM ESTERS NO ADDITIONAL EXAMPLES

SECTION 144:

HALIDES AND SULFONATES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES

SECTION 145:

HALIDES AND SULFONATES FROM HALIDES AND SULFONATES n-CgH17I, KF , GUI

CICF~02Me

-

C&I&F3

Cd12, HMPA , 120°C, 8h

Chen. Q-Y,; Duan, J.-X. Tetrahedron Lett., 1993, 34, 4241

SECTION 146:

+ CO2 + MeCl

77%

HALIDES AND SULFONATES FROM HYDRIDES

a-Halogenationsof aldehydes,ketonesand acidsare found in Sections338 (Halide-Aldehyde),369 (Halide-Ketone),359 (Halide-Esters)and 319 (HalideAcids).

BrF3, Br2 , O*C

Br Rozen, S,; Lerman, 0. J. Org. Chem., 1993, 58, 239

t

OMe

BP-(=)-OMe

CH2C12,MeOH 90% Bisawa. SC,; Rao, R. Synth. Commun., 1993, 23, 779

(t

PyH Br3, THF NJ32

\--I/

&eves.

W.P,; King II, R.M. Synth. Commun., 1993, 23, 855

87% (19:68 o:p)

Section 147


174

-

NBS/cat. HZSM-5 OMe

cc4

XeF2, MeCN ,25OC, 6h /

CHO

FQ

CHO

I H Wang, J.; Scott. AJ, Tetrahedron Lett., 1994, 35, 3679

’c’ \-/

I H

NH4VO3, H202, KBr 2 phase (H201CHCl3) ,25OC

*

35%

/- \ \r *

50%

Bf

\/ 9 9 0

Conte, V.; Di Furia. F,; Moro, S, Tetrahedron Lett., 1994, 35, 7429 I2

I

Qm03)2

I

CH2C12

52%

20°C , 14h

Bachki, A.; Foubelo, F.; Yus, M, Tetrahedron, 1994, SO, 5139

(t (t

HgO-120, CHg12 OBn *

\/

&jto.

$=)-OBn

87%

L; Hatakeyama, T.; Takeo, M.; Suginome, H. Synthesis, 1995, 1273 NBS , AcOH , ultrasound, 6h OMe * ..~-(=)-OMe

\/

92%

Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan. K,V, Synth. Commun., 1995, 25, 2401

SECTION 147:

HALIDES AND SULFONATES FROM KETONES CF2Br2,Zt-t

IL

F

u. C.-M,; Qing, F.-L.; Shen, C.-X. J. Chem. Sot., Perkin Trans. l., 1993, 335

Section 150

Halides from Misc.

175

SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLES

SECTION 149:

HALIDES AND SULFONATES FROM ALKENES

For halocyclopropanations,seeSection 74E (Alkyls from Alkenes). HCl , SiO2 Cl 62% 0 Kn]DD. P.J,; Daus, K.A.; Tubergen, M.W.; Kepler, K.D.; Wilson, V.P.; Craig, S.L.; Baillargeon, M.M.; Breton, G.W. J. Am. Chem. Sot., 1993, 115, 3071

0I

ma.

F

KHF2 , SiF4, rt

79%

M; Shibakami, M.; Kurosawa, S.; Arimura, T.; Sekiya. pb,J. Chem. Sot. Chem.

Commun., 1995, 1891

SECTION 150:

Ph-

N=N-N

HALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS

3

12, CH212,80°C ,4h

w

Ph-I

>98%

Wu, 2.; Jvfoare; J& Tetrahedron Lett., 1994, 35, 5539

m

S

S

Fz,Iz,MeCN,rt +

db ‘\

Chambers.;-;

I’

L /\

F

I’

52% Atherton, M. .I. Chem. Sot. Chem. Commun., 1995, 177

SOC12,DMF , 100°C 81% C~H25S03Na w325Cl Carlsen, P.H.J.; Rist, 0.; Lund, T.; Helland, I. Acta Chem. Stand. B., 1995, 49, 701


176

Section 153


CHAPTER

11

PREPARATION

OF

HYDRIDES

This chapter lists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen: e.g. RCH2X + RCH2-H or R-H.

SECTION

151: HYDRIDES

FROM

ALKYNES

NO ADDITIONAL

SECTION

152: HYDRIDES

FROM

EXAMPLES

ACID DERIVATIVES

This section lists examples of decarboxylations (RC02H + R-H) and related reactions. NO ADDITIONAL

SECTION

153: HYDRIDES

FROM

EXAMPLES

ALCOHOLS

AND THIOLS

This section lists examples of the hydrogenolysis of alcohols and phenols (ROH + R-H). 1. (Bu3Sn)p, To1 , reflux , Id (90%)

QH2hoH

2.2 eq. EtNCO

3. Et$iH , PhH , 140°C 0.05M , benzoyl peroxide (70%) Nishivama. K,; Oba, M.; Ishimi, M.; Sugawara, T.; Ueno, R. Tetrahedron

Ph-OH

1. [PPh3/rf20] , CH2C12 2. NaBH4, rt

3.1NHCl Hendrickson. JB,; Singer, M.; Hussonin, Md.S. J. Org. Chem.,

Wustrow. D.J%;Smith III, W.J.; Wise, L.D. Tetrahedron

* 1993,

ktt.,

1993,

Phn 87% 58, 6913

L&t., 1994, 35, 61

34, 3745

Section 157

Hydrides from Amines

H u;

Cusack, K.P.; Kwochka,

H W.R. Tetrahedron Lett., 1994, 35, 1477

PPh3, Et.$IBr , MeCN

CH3-(CHd9-QH

177

*

e’

C&---W2)g---H

94% Maeda, H.; Maki, T.; Eguchi, K.; Koide, T.; Qhmori. H, Tetrahedron Lett., 1994, 35,4129 CBH17-OH

1. MeCON=C=S

w C8Hl~ 2. Ph$iH , AIBN , 80°C, 10 min

48~83%

Oba, M.; Nishivama, K, Synthesis, 1994, 624 Also via: Section 160 (Halides and Sulfonates).

SECTION

154: HYDRIDES

FROM

ALDEHYDES

For the conversion RCHO + R-Me, etc., see Section 64 (AIkyls from Aldehydes). NO ADDITIONAL

SECTION

155:

HYDRIDES FROM AND ARYLS NO ADDITIONAL

SECTION

156: HYDRIDES

FROM

EXAMPLES

ALKYLS,

METHYLENES

EXAMPLES

AMIDES


SECTION

157: HYDRIDES

FROM

AMINES

This section lists examples of the conversion RNH2 (or R2NH) -+ R-H.

e- , TI-IF/HzO ,60% HNO3 67%

Tpfii. S,; Okumoto, H.; Satoh, H.; Minoshima, T.; Kurozumi, S. SynZett, 1995, 439

178


SECTION

158: HYDRIDES

FROM

Section 158

ESTERS

This section lists examples of the reactions RC02R’ + R-H and RCO2R’ + R’H, HO \\

+ UT.;

Pd(acac)z , PBu3 , rt PhH ,3h

.

(alkyne:allene = 99: 1)

CSh7

Matsumoto, T.; Kawada, M.; Tsuii. J, Tetrahedron

$=

J$

SMe

H

*

II other initiators

34, 2161

hv (tungsten lamp) Bu$nH , 0°C

S

l-BflqSi()i

Lett., 1993,

f-l

I

34,

2733

u-o’Ny

were .also used

Barton, D.H.R.; parekh. S&; Tse, C.-L. Tetrahedron

Lett., 1993,

SMe 5 eq. PhSiH3, AIBN

toluene , reflux , lh Barton, D.H.R.; Jang, 0.0.; Jaszverenyi, J.Cs. Tetrahedron,

43

quant.

1993, 49, 2793, 7193

dcoxygenated cyclohexane AIBN , 80°C 99% Gimisis, T.; Ballestri, M.; Ferrer-i, C.; Chatgilaloglu. C,; Boukherroub, R.; Manuel, G. Tetrahedron

Lett., 1995, 36, 3897

Section 160

Ph

4

AC

TBAFex Hz0 , NM0 , THF , rt 1,3-propanedithiol Ph

Ph Ph

w 0

0 Uelo. M4; Okamura, A.; Yamaguchi, J. Tetrahedron

SECTION

179

Hydrides from Halides

HYDRIDES FROM THIOETHERS

159:

99%

Lett., 1995, 36, 7467

ETHERS,

This section lists examples of the reaction R-O-R’ +

Me Hamel. P,; Zajac, N.; Atkinson, J.G.; Girard, Y. Tetrahedron

EPOXIDES

AND

R-H.

Lett., 1993, 34, 2059

5 eq. Ni2B , MeOH-THF t

C 11H23-S-Ph

I

2 NiBr2+

6 NaBH4

__I_)

Ni2B

90%

c 1 lH24

I

Back. T.G,; Baron, D.L.; Yang, K. J. Org. Chem., 1993, 58, 2407

0

DMN* , ascorbic acid , iPr0H hv,3h

SePh &Q&Y.

DMN*

= photoactivated

*

a=’

1,5-dimethoxynaphthalene

85% Cr,; Rao, K.S.S.P.; Sekhar, B.B.V.S. J. Chem. Sot. Chem. Commun., 1993, 1636

SECTION

160:

HYDRIDES

FROM

HALIDES

AND SULFONATES

This section lists the reductions of halides and sulfonates, R-X + R-H.

57% HI, 25OC, 15 min

98%

Wll Wll

Br Penso. M,; Mottadelli,

S.; Albanese, D. Synth. Commun., 1993, 23, 1385

180

Compendium

of Organic Synthetic Methods, Vol. 9

Section 160

Br\ MeLi,

THF , -105OC

52%

b-

Br

% Grandjean, D.; pale. P, Tetrahedron

L&t., 1993, 34, 1155

M+ B:i,-,:::“;HcHLH OCH2CH2CH2Br

2

an aryl

translocation

24% Lee. EJ Lee, C.; Tae, J.S.; Whang, H.S.; Li, KS. Tetrahedron

2

2

C3H7

61% Lett., 1993, 34, 2343

OH Cl

C

w

w

H

Cl

NaBHz(OCH2CH20Meh

Cl

NiCl2, MeOCHzCHzOH THF ,68OC, 2h

\

I

Cl Tabaei, S.H.; Pittman Jr.. CU, Tetrahedron

I

/

-4

Lett., 1993, 34, 3263

HC02H , Pd/C , toluene H20, NazCO, , 90°C Cl Cl Barren. J-P,; Baghel, S.S.; McCloskey,

quant. P.J. Synth. Commun., 1993, 23, 1601

PVP-PdC12, H2, 65OC ambient pressure , EtOH , NaOH PVP-PdC12 = palladium anchored on poly(N-vinyl-2pyrrolidinone) Zhang, Y.; Liao. S,; Xu, Y. Tetrahedron Lett., 1994, 35, 4599

0 \

I

/

quant.

Section 162

cti

181

Hydrides from Ketones

borohydride exchange resin , rt ,3h 0.1 Ni(OAc), , MeOH

17---Bf

Yoon. N.m, Lee, H.J.; Ahn, J.H.; Choi, J. J. Org. Chem.,

.

&I&I.

U,; Sanna, K.D. Tetrahedron

SECTION

161: HYDRIDES

Lett., 1994,

FROM

35,

*

CSH 17-H quant. 59, 4687

1994,

7861

HYDRIDES


SECTION

162: HYDRIDES

FROM

KETONES

This section lists examples of the reaction R2C-(C=O)R Et3SiH , BF3mOEt2, CHg12

+ R2C-H.

*

ph-

Ph mu.

Ph 92%

L Synth. Commun., 1994, 24, 1999

NaBHgN

, BFpOEt2, THF *

rt, 12h

‘(+(=)--c

130--(=)-\ 94%

Srikrishna. A,; Sattigeri, J.A.; Viswajanani, R.; Yelamaggad, C.V. Synlett,

1995,

93

OzC02Me

OH

1. ClC02Me

A

2, NaBH3

OH

I -OH 94x76%

. ltw. 36,5335

D,; Doecke, C.W.! Hay, L.A.; Koenig, T.M.; Wirth, D.D. Tetrahedron

Lett., 199%

182

Compendium

NHc~Me


1. Me$iCl

Section 165

NHCO2Me

, NEt3

2. Et$iH , Tic13 PhAA b Ph &CO,H ma--I Yato, M.; Homma, K.; Jshida. A, Heterocycles, 1995, 41, 17

NaCNBH3, THF BFyOEt;!, rt ,30 min 4

g5%

+

Me0 shna. A,; Viswajanani,

SECTION

.. 2) 85% (3 R.; Sattigeri, J.A.; Yelamaggad, C.V. Tetrahedron

163: HYDRIDES

FROM

SmI2, THF-HMPA

1995,

36,

NITRILES

This section lists examples of the reaction, R-C=N + isonitriles (R-N&). CN

tiff.,

R-H (includes reactions of

Ph

, 0°C

CN 97%

CN Ph 3 Hong, W.S.; Cho. Y.S,; Koh, H.Y. Tetrahedron Lett., 1995,

SECTION

164: HYDRIDES

FROM

ALKENES

NO ADDITIONAL

SECTION

165: HYDRIDES

FROM

H 36, 7661

EXAMPLES

MISCELLANEOUS

COMPOUNDS

Mg , EtOH , cat. HgCl2 P

rt

Lee, G.H.; Choi, E.B.; Lee, E.: Pak. C& Tetrahedron

98% Lett., 1993, 34, 4541


Section 166

Ketones from Alkynes

CHAPTER

183

12

PREPARATION

OF KETONES

SECTION 166: KETONES FROM ALKYNES

Cha. JS,; Min, S.J.; Kim, J.M.; Kwon, 0.0. Tetrahedron Lett., 1993, 34, 5113

. Tekeuchl.,

78% Yasue, H. J. Org. Chem., 1993, 58, 5386

MeCN , 760°C, 4h OMe CO)sCr

+ Me

(11:l ,33%) Kim, O.K.; 1;vulff. W.D%; Jiang, W.; Ball, R.G. J. Org. Chem., 1993, 58, 5572 0

Ph 1.10% c02(c0)8,

DME

2.20% P(OPh)3 , reflux

Iwasawa, N.; Matsuo, T. Chem. Lett., 1993, 997

0


Section 167

1. BrzBH*SMez 2. propylene glycol Br

X

Bu

* 3. CH2=CHCH2MgCl, THF , -78OC 4. HMPT , THF , 50°C, HMPA 5. oxidation Brown. H.r; Soundararajan,R. Tetrahedron Lett., 1994, 35,6963

Bu* 95%

MeReO3, H202, tOH Ph

=

Ph

*

Ph

Ph 4f 0

80%

Zhu, 2.; EsPenson.J.ltI, J. Org. Chem., 1995, 60, 7728

SECTION 167: KETONES FROM ACID DERIVATIVES

P

Ph

pAc1 TiCl&Zn ,3% HCl

-

p)$+;

+p;)=(;

69%

24%

Shi, D.; Chen, J.; Chai, W.; men. W,; Kao, T. Tetrahedron Lett., 1993, 34, 2963 1. (C6h3)2Zn

2. CuCN.2 LiCl

98%

Langer, F.; Waas,J.; -eI. Cl

P, Tetrahedron Lett., 1993, 34, 5261 e’ , Bu@3F4, rt

)

PTPh

80%

meCN 0 0 st. J.-C,; Pereira-Martins, E.; Troupel, M.; Perichon, J. Tetrahedron Lett., 1993, 34, 7571 1. (Me2N=CHCl)Cl, Py MeCN/THF 2 5eq NaN3 O°C * Pa 3:oYG rt ’ Affandi, H.; Bayguen, A.V.; J&&&W, Tetrahedron Lett., 1994, 35, 2729 pt(\/co2H

90% N3

185

Ketonesfrom Acids

Section 167

Me0 CgHllCOOH , (PhCO)20, Id 20% (Sic14+ 3 AgC104) CH2C12,rt Me0 T, BUZZ.Chem. Sot. Jpn., 1993, 66, 3729

Kitagawa, H.; m

&Z&&K.;

a

Ph

BU’n*SnBu3 Cl

Ph

Pd(PPh& , dioxane 100°C, 30 h

*

Ph+ 50%

0

Echavarren. A.M,; Perez,M.; CastaiIo, A.M.; Cuerva, J.M. J. Org. Chem., 1994, 59, 4179

0

1. (Ph0)2PON3, NEt3 dioxane , reflux 2.2 M HCl

t

?m

HW 0 w;

61% (2.83 cis:trans) Cowell, J.K.; Harris, L.J. Tetrahedron Lett., 1994, 35, 3883

.

0I \ 0

t-BuCl/Li/ ultrasound Liofl

, THF

76% Aurell, M.J.; Einhom, C.; Einhom, J.; Luche. J.L. J. Org. Chem., 1995, 60, 8

PhC02Li

iPrC1, Li , THF , ultrasound, rt

*

63% ’ Aurell, M.J.; Danhui, Y.; Einhom, J.; Einhom, C.; Luche, J.L, Synlett, 1995, 459

186


P

OH

NaI04, MeOH, TEBA

Phx

CO2H Kore, A.R.; Sagar,A.D.; &&&&. 0

92% * DB-18-c6 Ph-L Ph M.m Org. Prep. Proceed. Int., 1995, 27, 373

Ph

* Cl

Han, Y.; Fang, L.; Tao, W.-T.; m.

Cl

0

[PhJGaBuJLi, THF-hexane , 0°C

4f

Cl

Section 168

82%

Ph

Y.-Z4 Tetrahedron Lett., 1995, 36, 1287

Ph

PhMgBr , CuBr , LiBr , THF , 0°C

0

Ph

75%

0

Babudri, F.; Fiandanese,V.; Marchese.G; Punzi, A. Tetrahedron Lett., 1995, 36, 7305

m.

a

EtMgBr , Ni(dppe)Clz 70%

Ph * Cl PhL C,; Aronica, L.A.; Lardicci, L. Tetrahedron Lett., 1995, 36,9185

SECTION 168: KETONES FROM ALCOHOLS AND THIOLS 0.2% his-Ru catalyst, THF 65OC 99% w BackvaIl, J.-E.; Andreasson,U. Tetrahedron Lea., 1993, 34, 5459 1. t-B&OH, H+ *

Ph

2. DBU

80x58% Antonioletti, R.; Arista, L.; Bonadies, F.; Locati, L.; 8cett.t-i.A, Tetrahedron Lett., 1993, 34, 7089 !

1. RuC13.nHz0 , Co(OAch.4 Hz0 2. ;i;k-;,&Ho, 2o”c =c )

Murahashl.. S.-L; Naota, T.; Hirai, N. J. Org. Chem., 1993, 58, 7318

89%

187

Ketonesfrom Alcohols

Section 168

L

H

0.05 Cr03 ,3 eq. 70% t-BuOOH

96%

CH2C12, rt

Ph Muzaft.1; Ajjou, ANA. Synthesis, 1993, 785 0

1. Co(Imd)2 , EtOAc Ph Ph P LH 2. imidazole , CH2C12 0 68% S.-L; Park, D.-C.; Rho, H.-S.; Han, S.-M. Synth. Commun., 1993, 23, 2219

d

OH PDC , Celite , CH2C12

\

I

25OC, Id

/

55%

Bijoy, P.; Subba Rao. G.S.R,Synth. Commun., 1993, 23, 2701 Cal37

PhI=O ,;(NO&

, DCE

z&l37

OH aldehydescan also be formed quant. Yokoo, T.; Matsumoto, K.; Oshima. K.: UtimoK. Chem. Lett., 1993, 571

(t

V205 , Z1-02, toluene 0

OH llO°C, 6h

-o=

aldehydescan also be formed Nakamura, H.; Matsuhashi, H.; Arata, K. Chem. L&t., 1993, 749

-Q5

88%

5% CoSANSE, MeCN 60070°C, 02, 17h -

-Q+

CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; Iabsl. Tetrahedron Lett., 1994, 35, 4007

0

72%

188


Phi ,3% Pd(OAc)2, DMF

Section 168

Ph+O

w

3 eq. KOAc , 80°C, 3d

40%

Larock. RC,; Yum, E.K.; Yang, H. Tetrahedron, 1994, 50, 305

9 02

OH

(t

0

79%

CoSANSE * o= CoSANSE = chiral cobalt catalyst IQ&a, S.J.S.; Punniyamurthy, T.; Iqbal. J, Tetrahedron Lett., 1994, 35,4847

9 J+ z

t-B&OH, EhNOH , rt [OsO4] , aq. t-BuOH ,

fi

HO

i k

1 OH Beck, C.; Seifert. & Tetrahedron Lett., 1994, 35, 7221 0.5% Ru complex ,20% Co complex 0.5 02 , toluene , 1OOOC,36h 87% 2,5-dit-butyl-1,4-benzoquinone

0 OH Wang, G.-Z.; Andreasson,U.; Backvall. J.-E, J. Chem. Sot. Chem. Commun., 1994, 1037 cat. PdC12, cat. Adogen 464 9.3h, Nag03 , DCE , reflux

A&Mohand,

t-B.=-(-}=O

also for primary alcohol + aldehydes S.; Henin, F.; Muz . J, Tetrahedron Lett., 1995, 36, 2473

“;;;;t”,;OAc

)

t-B+(-)=0 96%

Murahashi. S-I,; Naota, T.; Oda, Y.; Hirai, N. Synlett, 1995, 733

189

Ketonesfrom Aldehydes

Section 169

OH Co(acac)3,02, MeCN ,75’C

93% O Iwahama, T.; Sakaguchi,S.; Nishiyama, Y.; Ishii. Y, Tetrahedron Lett., 1995, 36, 6923

6D

Bacillus stearothemophilus

‘4 %

heptane

*

64

0 49% 100%ee (lS,SR) Fantin, G.; Fogagnolo, M.; Giovannini, P.P.; Medici. A; Pedrini, P.; Poli, S. Tetrahedron Lett., 1995, 36, 441 OH

‘OH

0

cat. CoC12(PPh& , t-BuOOH /

93%

DCE , heat, 4.5h

Ph

aldehydescan also be formed Dyer. &; Varghese, J.P. Synth. Commun., 1995, 25, 2261 H

L

e’ , RuO2, aq. MeCN , Bu,$JOH

89%

Bu$JBr Ph Torii, S.; Yoshida, A. Chem. Lett., 1995, 369 RelatedMethods: Section48 (Aldehydesfrom Alcohols and Phenols).

SECTION 169: KETONES FROM ALDEHYDES

0.05 Rh(R-BINAP)ClOd CH2C12,rt ,30 min

(3

97) 81% (>99%ee3S,4S)

Wu, X.-M.; Funakoshi, K.; Sakai. K, Tetrahedron Lett., 1993, 34, 5927

190


Section 169

71% Punniyamurthy, T.; Kalra, S.J.S.; Qbal. J, Tetrahedron Lett., 1994, 35, 2959

PhCHO

1. t-BuMe$iCBrzLi 2. set-BuLi

, -78OC + rt

3. PhCHO 4. HMPA Shinokubo, H.; Oshima. K.: IJtimotu

0

*

PhkPh

5g%


59% (78% ee , S) Barnhart, R.W.; Wang, X.; Noheda, P.; Bergens, S.H.; Whelan, J.; Bosnich.B,. Am. Chem. sot., 1994, 116, 1821 Me$iCBr3

PhCHO

, CrBq/LiAlHq

THF , 60°C

mn.

D.M.; Comma, P.J. Synlett, 1994, 663

PhCHO CH(OEt)3, H+ , THF

Katritzkv.

2. BuLi, THF , -78OC 94% 3. EtBr 4. H+ A.R,; Lang, H.; Wang, 2.; Zhang, 2.; Song, H. J. Org. Chem., 1995, 60, 7619 C&I $xCpCl

,20% ZnBr2

PhCHO

*

PhCHO *

THF ,3h ,25OC Zheng, B.; Sreb&

M, J. Org. Chem., 1995, 60, 3278

Section 171

Ketones from Amides

SECTION 170:

191

KETONES FROM ALKYLS, METHYLENES AND ARYLS

This section lists examples of the reaction, R-CH2-R’ -3 R(C=O)-R’. 5% CoSANSE , MeCN Ph-

t

Ph

cat. 2-oxocyclopentene carboxylate 60°C, 15h, O2 CoSANSE = ~is(salicylidene-N-(methyl-3-hydroxypropionate))] Co Punniyamurthy, T.; IabaI. J, Tetrahedron Lett., 1994, 35, 4003

t’h

69%

OMe OMe

A@, Me$YBF3 CH2C12, -78OC+ rt 76%

Kiselyov, A.S.; m.

R.G, Tetrahedron Lett., 1995, 36, 4005

SECTION 171: KETONES FROM AMIDES

Me\

N I OMe

OMe I N\ Me

0 1.2 eq. PhLi Ph +

2 . H+

Ph 4f

0

75% O

Sibi. M.P,; Marvin, M.; Sharma, R. J. Org. Chem., 1995, 60, 5016 1.2.2 BuLi , -78OC cN-(

,Ph

t 2. AcOH 3. K,C03,65°C

,.ji\

ph

82% Brandange, S.; Holmgren, E.; Leijonmarck, H.; Rodriguez, B. Actu Chem. &and. B., 1995, 49, 922

\ G

N-

1.2 eq. PhLi t

C02Et 2. H30+

Ph Prakash, G.K.S.; York, C.; Liao, Q.; Kotian, K.; Qlah. G.A, Heterocycles, 1995, 40, 79

95%

192


Section 172

2 eq. EtAIC12, rt , 12h Ph Ph7

N I

56%

Ph

CH2Q

so2

Iwama, T. Tetrahedron Lett., 1995, 36, 245

-T.;

0

PhMgBr

PhK

68% Ph

. Kashlma. CJ Kita, I.; Takahashi, IS.; Hosomi, A. J. Heterocyclic Chem., 1995, 32, 25 REVIEW:

“Chemistry of N-Methoxy N-Methyl Amides. Applications in Synthesis.A Review,” S M.P. Org. Prep. Proceed. Int., 1993, 25, 5

SECTION 172: KETONES FROM AMINES 1. “X” 2. H30+

t

3 = H

40% X = octane,230°C ,2h X = t-BuOK./BuLi/THF/-50°C ,2h 73% Sprules, T.J.; Galpin, J.D.; Macdonald, D, Tetrahedron Lett., 1993, 34, 247

kc@7

9 W04 9ether 25OC, lh

Harris, C.E.; Lee, L.Y.; Dorr, H.; Singaram. B, Tetrahedron Lett., 1995, 36, 2921

75%

Section 174

Ketonesfrom Ethers

193

/OH o= % )=c

7% 86% Gao, J.; Hu, M-Y.; Chen, J-x.; Yuan, S.; Chen, W-x Tetrahedron L&t., 1993, 34, 1617

86%

Pa

Lett., 1993, 34, 3951

Section 177

Ketonesfrom Ketones

d

Tick, CH&

199

92%

lIllIIIIIISi(i~)3

-78OC + -2OOC

& Kniilker. H.-J; Graf, R. Tetrahedron Let?., 1993, 34,4765

(5: 1 anti:syn)

98~72%

pandey. G,; Krishna, A.; Girija, K.; Karthikeyan, M. Tetrahedron Let?., 1993, 34,663l 1. LiN(TMS)z A/q/\

:-.:;:,.,

,4h

+ + 95%

Reetz.;

Haning, H. Tetrahedron Let?., 1993, 34, 7395

Cossy. J,; Furet, N. Tetrahedron Let?., 1993, 34, 8107

0

kEi:%ir?-t, 18h ) &J~.I+ 56~~~lohexmo

J&&s. R&; Taylor, S.R. .I. Org. Chem., 1993, 58, 4469

Cahlez. G,; Figadbe, B.; Cl&y, P. Tetrahedron Let?., 1994, 35, 3065

Section 177


200

,,,,\\\I”’

TMS

4

CF$&Ag

, Me1 -CH2C12,-78OC+ rt

+

4

..

(6 1 P, Tetrahedron Lett., 1994; 35, 367

Angers, P.; we.

rc 1)

Chen, L.; Gill, G.B.; Pattenden.G, Tetrahedron Lett., 1994, 35, 2593 1. MeLi 2. MnC12 Ph

3. PhCH2Br ; Chau, K.; Cl&y, P. Tetrahedron Lett., 1994, 35, 3069 0 0

BuA

MeCHN2 , Me3Al ,O”C CH2C12, lh

Bu

Maruoka, K.; Conception, A.B.; -to.

/I & #

*

55%

Me I& J. Org. Chem., 1994, 59,4725

2.5 eq. BuySnH , AIBN *

Cl

0T

Bu Bu K,

8h slow addition

q 0 Dowd. PJ Zhang, W.; Mahmood, K. Tetrahedron Lett., 1994, 35, 5563

57%

0

78%

201

Ketonesfrom Ketones

Section 177

SC-1 , Ni2B , H2 (1 atm) 0

*o=O

+

Q-OH

(>99

: B, Tetrahedron Lett., 1994, 35, 5595

BeIisle, C.M.; Young, Y.M.; S

SiMe3

Ph

Ph

Ph

1) >99%

Ph

0

Yb,THF,40°C,2h

-

CHPh;!

‘r(

Ph

Ph

+

OH 68% 29% Taninuchi. Y,; Nagafuji, A.; Makioka, Y.; Takaki. K.: Fujiwara. Y, Tetrahedron Lett., 1994, 35, 6897 0

&

hv’NEt3

t

0

&

48%

Kirschberg, T.; Mat@y. J, Tetrahedron Lett., 1994, 35, 7217 Ph Rh2(O$R*)4, CHgl2, -2OOC,2h 0 Ph

N2

64%

(77% ee , S) Watanabe,N.; Ohtake, Y.; &phimoto. S,; Shiro, M.; Ikegami, S. Tetrahedron L&t., 1995, 36, 1491

Ph

Ph

CHO

Ph *

S 2277

Ph

84%

cat. TMSOTf , rt , CH#2,5h 0 SE; Awachat, M.M.; Kelkar, S.V. Tetrahedron L&t., 1995, 36,

Section 179


202

0

C&12, SmI2, TI-F ,5h

61% -s.;

Tsuchimoto, T. Tetrahedron Lett., 1995, 36, 5937 Bu$nCl - NaBH3CN, AIBN SO;?Ph

t-BuOH , heat

86% Giovannini, R.; Petrini. M,Synlett, 1995, 973 REVIEW: “Organotin Enolates in Organic Synthesis. A Review,” Shibata. I,; Baba, A. Org. Prep. Proceed. Int., 1994, 26, 123 Related Methods: Section 49 (Aldehydes from Aldehydes).

SECTION 178: KETONES FROM NITRILES NO ADDITIONAL

EXAMPLES

SECTION 179: KETONES FROM ALKENES

k

1,4-dimethoxybenzene(sensitizer) hv , MeCN , 12h, rt

Ph B.

0 -

> Ph

90% conversion b-p-d

IJ.T,; Sridhar, M. Tetrahedron Lett., 1993, 34,434l

I \ + (x S

GTign.;

I

TlOAc , CO, MeCN 80°C, 16h 10% [Pd(OAch/2 PPh3]

I \ L s

-

75% Khalil, H.; Levett, P.; Virica, J.; Sridharan, V. Tetrahedron Lett., 1994, 3.5, 3197

Section 179

Ketones from Alkenes

203

10% Pd(OAc), ,20% PPh3 Et4NC1 , CO

88% Gring.;

Redpath, J.; Sridharan, V.; Wilson, D. Tetrahedron L&t., 1994, 35, 4429 1. Et2BHaSMe2 , ether, 25OC 2. Et$n , neat, O°C

Ph 3. CuCN.2 LiCl , THF , O°C 4. PhCOCl d Langer, F.; Devasagayaraj, A.; Chavant, P.-Y.; mochel. P, Synlett, 1994, 410

84%

Me3SiN3, CH2C12,CrQ 59% Reddy, M.V.R.; Kumareswaran, R.; m.

Y.D. Tetrahedron L&t., 1995, 36, 6751

1. [CK12*THF/PhEt2N:BH3, ClOH2w/

PhH , CO]

: ;5:r36h . 9 4. H202, NaOH , NaOt-Bu

C~H2JLH. 70%

Rao, M.L.N.; Periasamv. M, Tetrahedron Lett., 1995, 36, 9069

0 A

9 w=ma *

2 PPh3, DCE d (>20 Lautens. MJ Edwards, L.G.; Tam, W.; Lough, A.J. J. Am. Chem. &..

d 1) 99% 1995, 117, 10276

204


Section 180

1. Cl$=C=O 2. Bu$nH , AIBN 85% (84:16) Dowd. P,; Zhang, W.; Geib, S.J. Tetrahedron, 1995, 51, 3435 See also:

Section 134 (Ethers from Alkenes). Section 174 (Ketones from Ethers).

SECTION 180:

KETONES FROM MISCELLANEOUS COMPOUNDS

Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from AIkenes). Ph

>

5) 0

9m

Ph

9 C&Cl2

0 20°C , 30 min 92%

TFP= l,l,l-trifluoropropane Ahamura, A.; Curci, R,; Edwards, J.O. .I. Org. Chem., 1993, 58, 7289

#-(-)=NoH ooc,loi?~ * -(-)=o acetone ,

80% Olah. G.A,; Liao, Q.; Lee, C.-S.; Prakash, GKSJynlett, Ph

O3 , CH2C12, -2OC ,2h

1993, 427

Ph

N-OH * > Ph Yang. Y.; Li, T.; Li, Y. Synth. Commun., 1993, 23, 1121 N---NHTs

PhI(OA&

> Ph

0

95%

, MeCN , rt , 10 min w

Ph

Ph Me

Me 87% Zeng, H.; Chen. Z-C, Sytih. Commun., 1993, 23, 2497

Section 180

J

Ketonesfrom Misc.

205

TS-1, H202, MeOH, 4h

-NHTS

84%

TS-1 = titanium silicate molecular sieves Kumar, P.; Hegde, V.R.; Pandey,B.; Ravindranathan. T, J. Chem. Sot. Chem. Commun., 1993, 1553 Ph

Ph

KMn04, aq. MeCN , rt , lh N-OH

0 *

95%

k=

Wali, A.; Ganeshpure,P.A.; Satish. S&11. Chem. Sot. Jpn., 1993, 66, 1847 NO2

NflHdH202

K2CO3, MeOH Ballini. R,; Bosica, G. Synthesis, 1994, 723 NNHcoNH2

hJ-

PhI(OAc);?, aq. MeCN

0 w

80%

P Me Chen, D.W.; Chen, ZC, Synthesis, 1994, 777

N-NMe2

Me

@uqN)2Sz& 7DCE reflux , lh

Choi, H.C.; m.

&Synth.

N-OH P +

Commun., 1994, 24, 2307

Bentoni te/AgzC03 , PhH

0 t

50%

Ph *

reflux ,4h Me Me Sanabria, R.; Miranda. R,; Lara, V.; Delgado, F. Synth. Commun., 1994, 24, 2805

d=

N-NHTs

(Bu4N)2S208, DCE , reflux 0

lh =c

95%

0

Chen F,; Yang, J.; Zhang, H.; Guan, C.; Wan, J. Synth. Commun., 1995, 25, 3163 REVIEW:

“Macrocycle Synthesis:Cyclic Ketones,Ketoalkenes,Diketones and Dienes of Ring Size C21 Dang, Y. Org. Prep. Proceed. In?., 1993, 25, 309 to &jr” EQ-;

Section 180A


206

SECTION

180A: PROTECTION

OF KETONES

[Rh(MeCN)3(~phos)l Wfh

I7

acetone, rt ,4h

*

PhJL

90%

Me

\ / 9 * 00 o= .M, Tetrahedron Lett., 1993, 34, 8071 HS

SH

n ,-c

S

3m12

0

rt

S

92%

m

Y J Yu, Y.; Lin, R. Org. Prep. Proceed. Int., 1993, 25, 365

p-TsOH , PhH , reflux , cat. TMSI

9

DDQ 9H20 C&C12 95% McDon;tld. CL; Nice, L.E.; Kennedy, K.E. Tetrahedron Lett., 1994, 35, 57 MesSid\/\

0

SiMq OS iMe

CF$O$iMe3 , CH2C12 -78OC

o=

(--bti3

4

LiBF4, MeCN , heat 96% Lillie, B.M.; Avery, M.A. Tetrahedron Lett., 1994, 35, 969 AcCl ,2% SmC13 , rt * 15 min Wu. S.-H.; Ding, Z.B. Synth. Commun., 1994, 24, 2173

Section BOA

Protection of Ketones

207

cat. Pd(OAc)z ,2 NaOAc ,02 )

OSiMe3

58%

0

DMSO

o= Larock. R.c, Hightower, T.R.; Kraus, GA.; Hahn, I?; Zheng, D Tetrahedron Lett., 1995, 36, 2423

S

S

Se02 , AcOH , rt ,25 min

0 .

98%

aldehydes can also be used Phx outounian. S.A, Synthesis, 1995, 39

CuSO4/SiO2, CHC13 20°C ,2d

Caballero, GM.; Gras. E.G,Synth. Commun., 1995, 25, 395

Kurihara, M.; Miyata, N. Chem. L&t., 1995, 263

See Section 362 (Ester-Alkene) for the formation of enol esters and Section 367 (Ether-Alkenes) for the formation of enol ethers. Many of the methods in Section 6OA (Protection of Aldehydes) are also applicable to ketones.


208

Compendium

CHAPTER

13

PREPARATION

SECTION

OF

181: NITRILES

FROM

NITRILES

ALKYNES

NO ADDITIONAL

SECTION

182: NITRILES

FROM

183: NITRILES H

A

W-h

FROM

MezC(CN)OH

EXAMPLES

ACID DERIVATIVES

NO ADDITIONAL

SECTION

EXAMPLES

ALCOHOLS

AND THIOLS CN

, MeCN , DEAD

58%

/ C6Hl

Me

. ilk. EL& Synth. Commun.,1993, 23, 2481

SECTION

184: NITRILES

FROM

WCHO

MeOH, rt

* 2. “crude” , MeOH , O°C 2.4 MMPP6 Hz0

aCN 88%

MMPP = magnesium monoperoxyphthalate R.; Gasch, C.; Lassafwm J-K; Llera, J-M.; Wzquez, TetrahedronLett., 1993,34, 141

Ferbdez,

185:

NITRILES ARYLS

Me

ALDEHYDES

1. Me$WI-I2,

SECTION

Section 185


FROM

NO ADDITIONAL

ALKYLS, EXAMPLES

J.

METHYLENES

AND

Section 190

SECTION

Nitriles from Halides

186: NITRILES

FROM

AMIDES

Ph

2 PPh3, 2 cc14 Ph

e

209

97% CN H other reagents are also given that lead to this conversion Waers. M.A.; Hoem, A.B.; Arcand, H.R.; Hegeman, A.D.; McDonough, C.S. Tetrahedron Lett., 1993,34, 1453 0

PhA

*

3 NEt3

Ag20, Et1, PhH,25OC

Sznaidman,M.L.; Crasto,C.; Hecht, SM. Tetrahedron

/\I(

NH2

0

Correia.J, Synthesis,

SECTION

Ph-CN

(dark), MS 4A, 12h

NH2

Bu

y-

1994,

Lett., 1993,34, 1581

NaOCl, NaBr, PhWH20 w TBAHS04, Na$?Oe12H@ 1127

187: NITRILES

FROM

82%

Bu-C-N

=

55%

AMINES


SECTION

188: NITRILES

ph-OAc

FROM

ESTERS

Me$iCN,

WPPh& *

THF , reflux ,16h

PhMCN 98% (E.-Z, >9:1)

Tsuji. Y,; Yamada,N.; Tanaka,S. J. Org. Chem., 1993, 58, 16

SECTION

189:

NITRILES FROM THIOETHERS

ETHERS,

EPOXIDES

AND


SECTION

190: NITRILES

I

FROM

HALIDES

AND SULFONATES

1. BuLi, THF, -1OOOC 2.ZnI2 , -loo”c + o”c 3. TosCN, -78OC+ rt ,3h

CN -

Klement,I.; Lennick,K.; Tucker,C.E.; Knochel,P, Tetrahedron

0

84%

Lett., 1993, 34,4623

210


MezC(CN)OH , MeCN , TMG *

MBr

MCN

TMG= 1,1,3,3-tetramethylguanidine Dowd. P,; Wilk, B.K.; Wlostowski, M. Synth. Commun., 1993, 23, 2323 TiC4,

9-

PhgH-CN 93%

Ziener. HE,; Wo, S. .I. Org. Chem., 1994, 59, 3838

191: NITRILES

FROM

HYDRIDES

NO ADDITIONAL

SECTION

192: NITRILES

71%

TMSCN , CH2C12 , O°C

PhgHCl

SECTION

Section 194

FROM

EXAMPLES

KETONES

1. secBuLi, TMSCl 2. secBuLi1

CN

0

ck= t-Bu

89%

3. Me1 4. NaOMe

alsoworkswith aldehydesubstrates Santiago,B.; u.

A.& Tetrahedron

A 0

Ph

Lett., 1993, 34, 5839

1.Me(Cl)AlNH;! * CF3

Kende.AS,; Liu, K. Tetrahedron Lett., 1995, 36, 4035

SECTION

193: NITRILES

FROM

NITRILES

Conjugatereductionsand Michael alkylations of alkene nitriles are foundin Section74D (Alkyls from Alkenes). NO ADDITIONAL

SECTION

194: NITRILES

Ph----CN

2. t-BuOK

FROM

EXAMPLES

ALKENES

NO ADDITIONAL

EXAMPLES

85%

Section 195

SECTION

Nitriles from Misc.

195:

NITRILES FROM COMPOUNDS

211

MISCELLANEOUS

83%

Dandgar.B.P%;Jagtap,S.R.; Ghodeshwar, S.B.; Wadgaonkar,P.P.Synth.Common., 1995,25, 2993


212


CHAPTER

14

PREPARATION

SECTION

Section 196

196: ALKENES

OF

FROM

Ph-C=r-Ph

ALKENES

ALKYNES

, DMF , 120°C

10%Pd(OAc)z,20% PPh3 2 TlOAc ,36h Griw Q, Kennewell,P.; Teasdale,A.; Sridharan,V. Tetrahedron Let?., 1993, 34, 153

xz OTs

w;

.

(PhMe$i)$uCNLi2 THF , -78OC -3 rt

de Marigorta,E.M. Tetrahedron Let?., 1993, 34, 1201 1. *&

C3H-W7

vrt

C3H7

$7

Cp2Zr(CH2=CH2). Id

* -c, 68% 2. H+ . Takahashl,T,; Kondakov,D.Y.; Suzuki,N. Tetrahedron Let?., 1993, 34, 6571

(Me$i)$iH , hv (sunlamp) 2h, hexane 70%

Pattenden.G,; Schulz,D.J. Tetrahedron

Let?., 1993, 34, 6787

Section 196

Alkenes from Alkynes

I \

NO2

+

0

I

10% Pd(OAc)z 20% PPh3 , DMF TI(OAc) , 130°C 18h

I b Et&C

‘C02Et Sridharan, V. Tetrahedron

Brown, S.; Clarkson, S.; Grign.;

Le ‘tt., 1993,

34,

157

1.Cp$r(H)Cl , CHg12 20°C ,20 min w 2.5% AgC14

10min TBDMSO Wiof. P,; Xu, W. .I. Org. Chem., 1993, Ph

/-\

0 0 58,

825

TBDMSd

92%

/

1. t-BuLi , pentane/ether 2. -78OC + rt + -78OC )

I

0

99% z) Lett., 1994,

J.-F, Tetrahedron

hv , 1%CpCo(CO)2, PhH, heat

-

Stammler,R.; Malacria. SiMe3

35, 6677

-Bu-Bu

Brasseur,D.; Jestin,J.-L.; Nom

C02Me

1994,

23) 69% 54% de

1. Bu@Li , ether 2.2 eq. BuLi , -4OOC , Me2S 3. NH3/NH&l

/ Ph

35, 4669

35,

C02Me

b

93%

W Synlett, 1994, 92

1. Cp$rBu2, PMe3 2.35”C , Eto 9

5c Me$i3OEt

Et0

71%(53:47 cis:trans) 3. H30+ . Takahashl.; Kondakov,D.Y.; Suzuki, N. Chem. Lett., 1994,259 Ph

E

NiBr;?-Zn, diphos, H2

* phm g2% sakai. &; Takai, Y.; Mochizuki, H.; Sasaki,K.; Sakakibara,Y. Bull. Chem. Sot. Jpn., 1994, 67, 1984


216

Section 197

QSiEt3

OSiEt3 3% (PCy3)g12Ru=CHCH=CPh2 CHzC12, (0.6 M) ,2X

,8h

P tie Me Kim, S.-H.; Bowden,N.; mbbs. RcfL J. Am. Chem. Sot., 1994, I16, 10801 Me$iI , Me$n , dioxane SiMe3

95%

61%

5% Pd(PPh3)4,25OC,8 h Chatani,N.; Amishiro,N.; Morii, T.; Yamashita,T.; Murd. S,J. Org. Chem., 1995, 60, 1834 OSi(OEt)3 OH-

Me20%CpZTi(PMe&, HSi(OEt)3

-)&

Me 73%

Qowe. WL; Rachita,M.J. J. Am. Chem. Sot., 1995, I1 7, 6787 Br SmI2,THF , DMPU P2

Phd

= 83%

Zhou,2.; Larouche,D.; Bennett.

SECTION

197: ALKENES

Tetrahedron,

FROM

1995, 51, 11623

ACID DERIVATIVES

0.01PdC12(PPh&, PPh3 c6H’-C0

2H

P 250°C, N2

c6H1v

Miller. J.A,; Nelson,J.A.; Byrne, M.P. J. Org. Chem., 1993, 58, 18 M Cl

, Me$i-SiMe3 , toluene

5%Pd(dba)z, 80°C,4h

Obora,Y.; Tsuii. Y,; Kawamura,T. J. Am. Chem. Sot., 1995, 117, 9814

9840

section 199

SECTION

Alkenes from Aldehydes

198: ALKENES OH

FROM

217

ALCOHOLS

AND THIOLS

H-montmorillonite

dioxane c9H19~ + C9H19d (air free) . reflux ,6h 19) 91% (81 Santhi, P.L.; Siddiqui, M.F. Tetrahedron L&t., 19b3, 34, 1185 -

Kantam. OH

OH

1. SOCl;!, NEt3, 0°C rt NMe(OMe) 2.DBU,0°C + ~

Ph

NMe(OMe)

Ph

92%

T ee) (96.98% Bennani,Y.L.; m.

K.B. Tetrahedron Lett., 1993, 34, 2083 Mo(acac)s, dioxane, reflux

c lOH23

C10H23

OH -f

-

* (1

+ c1a2Y . 1) 92%

Prasad,A.D.; Santhi,P.L. Synth. Commun., 1993, 23, 4;

Kantam.;

phflp::::::’ wph-/c+ ,,/orr

Dorta, R.L.; SE.;

SECTION

73%

8%

Betancor,C. Tetrahedron Lett., 1994, 35, 5035

199: ALKENES

FROM

ALDEHYDES

Me 1.2 LDA Et0 2. PhCHO (>98:2 , E:z)

Coutrot.Ph,; Grison,C.; Gkardin-Charbonnier, C.; Lecouvery,M. Tetrahedron 2767

Lett., 1993, 34,


Section 199

MezCHzPPh3+ BrBuLi , THF , -78OC Ph

SiMes-Bu [94:6 E.-Z (>98%ee, R)]

Bhushan,V.; Lohray, B.B.; En&.

D, Tetrahedron Lett., 1993, 34, 5067

1. H2S, THF , -3OOC 2. NH2NI12 3. -3OOC ,4h C7Hl

seCHO

co1kizo, L .R.; Q&c

a

AC

4. MgS04, -3OOC 5. CaCO3, Pb(OAc)d -c7H-IliI 6. THF , reflux 7. PPh3, THF , reflux Jr.. F& J. Org. Chem., 1993, 58, 43 Cfl l~H0,Zr-t , CrCl3, DMFm

Br

56%(91:9E:Z)

Knecht, M.; Boland.W,Synlett,

1993, 837

CN

CH2(CN)2, CdI2,neat PhCHO heaat,5 min

*

95%

A Ph

CN Prajapati,D.; Sandhu.JS, J. Chem. Sot., Perkin Trans. l., 1993, 739 Bu+CH 2Br2 , 25°C Li , CrCl2, DMFII’HF

Me020CH0

‘,

Me02C/\/\/n/SnBu3 61%

w

D.M; Boulton,L.T.; Maw, G.N. Tetrahedron Lett., 1994, 35, 2231 wCH0

[PPh3=CHMe/I$2NaNTMS23 = *42% (1O:l Z:E)

Chen,J.; Wang,T.; aao. K, Tetrahedron

Lett., 1994, 35, 2827

SiMe3

(Me$i)2CBr2, CrC12 PhCHO &&on.

) DMF ,25”C

D.M,; Comina,P.J. Tetrahedron

84% Ph

Lett., 2994, 35, 9469

SiMe3

Section 200

AIkenes from Alkyls

E10*~-Lpp~3+ Cd-J

219

Br- , dioxane

QH13

13CHO

Ph& , hv , K2CO3, H20, 90°C, 2h

-

YCOEt

70% (78:22 E:Z)

2

(withouthv 12:18 E.-Z) Matikainen,J.K.; Kaltia, S.; Hase.T,SynZett,1994, 817 EtOzC\/sMe3

PhCHO,

DMSO t

EtO&-WPh

cat.CsF, rt + 100°C aed.

93%

M; Ozanne,N. J. Org. Chem., 1995, 60, 6582

SiMe3 PhCHO

t

80%

25OC Ph’+ N-4; Staszewski,J.P.; Fuk, D.-K. Tetrahedron Lett., 1995, 36, 3619

c

C02Et 1. KHMDS , THF, lh 5 eq. lg-crown-5,-78OC 0 w / \P 2. PhCHO I\ Ph PhO OPh Ic Tetrahedron

+ 4 Ph

..

(99 A&I.

EtOg

C02Et

1) 98%

Lett., 1995, 36,4107

C02H

Me3SiCH=C=O,BF3GEt2 PJCHO mk.

-/P

90% (1:l E.-z) T&; Zhang,Y.; Huang,J.; Smith, D.C.; Yates,B.E. Synth. Common., 1995, 25, 15 RelatedMethods:Section207(Alkenesfrom Ketones).

SECTION

ZOO:

ALKENES FROM AND ARYLS

ALKYLS,

METHYLENES

Thissectioncontainsdehydrogenations to formalkenesandunsaturated ketones,estersand amides.It alsoincludestheconversionof aromaticringsto alkenes.Reductionof arylsto dienesis foundin Section377(AIkene-Alkene).Hydrogenation of arylsto a.Ikanes and dehydrogenations to formarylsareincludedin Section74 (Alkyls from Alkenes).

220

Compendium


Section 203

CgK , THF

*

Weitz, 1.S.; wov&.

M1 J. Chem. Sot., Perkin Trans. I ., 2993, 117 Br Me0

A

2F

Pseudomonas cepacia AC1 100

OHC

OH

* OMe Artaud, I.; Tomasi, I.; Martin, G.; Petre, D.; Mansuy, D. Tetrahedron

SECTION

201: ALKENES

Related Methods:

FROM

ti:H CHO Lett., 1995, 36, 869

AMIDES

Section 65 (Alkyls from Alkyls). Section 74 (Alkyls from Alkenes). 1. PhLi, THF , 0°C 85%

Jurata, H.; Ekinaka, T.; Kawase, T.; gda, M, Tetrahedron

SECTION

202: ALKENES

Belier. aFischer,

SECTION

H.; Kiihlein,

203: ALKENES

n

FROM

AMINES

K. Tetrahedron

FROM

Lett., 1993, 34, 3445

Lett., 1994, 35, 8773

ESTERS

1% Pdz(dba)3-CHC13 ,2.2 HCOOH 2% chiral phosphine , dioxane 1,8-his-(dimethylamino)naphthalene 20°C ,22h :

%, ++H MeO,CO Me 96% (85% ee, R) . T,; Iwamura, H.; Naito, M.; Matsumoto, Y .; Uozumi, Y .; Miki, M.; Yanagi. J. w. Am. Chem. Sot.., 1994, 116, 775 02

Section 205

SECTION

AIkenes from Halides

204:

ALKENES FROM THIOETHERS

221

ETHERS,

EPOXIDES

Te , THF

OAc

I

OH

LiBHEt3 c Ph Ph DC,; Zhang, Y.; Discord& R.P. J. Org. Chem., 1994, 59, 1004

uenishi. J,; Kubo, Y. Tetrahedron

A

65%

Lett., 1994, 35, 6697

set-BuLi , -78OC+ rt ,90 min 76%

Bu

Bu

Gr

Doris, E.; Deschoux, L.; Mioskowski,

SECTION

AND

205:

ALKENES

C. Tetrahedron

FROM

Bu

Lett., 1994,

HALIDES

Bu 3.5, 7943

AND SULFONATES

Bu$nH , AIBN , Tol, reflux Ph Destabel,C.; Kilbum, J.D. Knight, J. Tetrahedron Lett., 1993, 34, 3151 9

.

nI \

..Li,TI-IF,rt,lh 2. ZnCl;!, THF , O°C-+ rt Br

w , THF ,66OC

m. 1993,

5% “Pd(PPh3)2” , 1Oh T&; Gilbert, A.M.; Huttenloch, M.E.; Min-Min, G.; Brintzinger, 34,

3551

H.H. Tetrahedron Lett.,

Compendium

222

Br

Me$i


MeLi,

Section 206

20°C 82%

-A %k siMe3 Br Bu Bu Baird. M.S; Dale, C.M.; AI Dulayym, J.B. J. Chem. Sot., Perkin Trans. I., 1993, 2

c14H16’-\

eq. MezS=CHz

, THF

L,

1373

C14h6

92% -1OOC + It AIcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5453 Br

1. CuCN.2 LiCl , DMPU CSH

-

17Zd

C8H1-

2. E-hexenyl iodide, 60°C ,12h

Bu quant.

Marquais, S.; Cahiez, G.; Knochel. P,Synlett, 1994, 849 Br Ph L WR.;

SmI2,THF,5min

Ph

= i Br Bessho, K.; Yanada, K. Chem. Lett., 1994, 1279

r

I Bu 3SnHPh

*

Phm

/

10% Pd/C , 10% CuI ,20% AsPh3 NMP , 80°C 75 Me0 Me0 Roth, G.P.; Farina, V.; Liebeskind, L.S.; Pena-Cabrera, E. Tetrahedron

C; Aronica, L.A.; Lardicci, L. Tetrahedron

SECTION

206: ALKENES

FROM

Ph

I

82%

Lett., 1995,

EtMgBr , THF , O°C

MaIan=

Ph 95%

36,

quant. Lett., 1995, 36,9189

HYDRIDES

For conversions of methylenes to alkenes (RCH2R’ + 200 (Alkenes from Alkyls). NO ADDITIONAL

EXAMPLES

RR’C=CH2),

see Section

2191

Section 209

223

Alkenes from Alkenes

SECTION

207: ALKENES

FROM

KETONES

65%

PhMe , 50°C

Me

Petasis. N.A; Bzowej, E.I. Tetrahedron

Lett., 1993,

34,

943

(Me0)2POCHgO2Me 0

(-)=yo2t% LiOH , THF , MS , reflux ,4h5c Cardilli, A.; Lattanzi, A.; Orelli, L.R.; Screttri. A, Tetrahedron

wsz; 3383

t-B+(-)=o -a.

$ ~~;;f;;~r2*

t-Bu-(-)=
newDiels-Aldercatalyst Kobwashi. S,; Hachiya,I.; A&i, M.; Ishitani,H. Tetrahedron Lett., 1993, 34, 3755

OTBS

ArN=Mo(OR)=CHRcatalyst

OTBS

PhH, 20°C,30 min 91% Fu, G.C.; Grubbs. R.H,J. Am. Chem.Sot., 1993, 115, 3800 2

Ph-

1%Mo[OC(CF&Me]2(NAr)CHCMe2Ph * pl/%/+c6HD

+

89%

W-h~

Qowe. W.E,; Zhang,Z.J. J. Am. Chem. Sot., 1993, 115, 10998

&

1.PhBr , THF , Pd(PPh& NaOH , reflux , 12h 2. NaOH, Hz02

P -

8,

siM!e3

L&t., 1994, 35, 27 w17

SmI2 PhH/HMPA, rt , 10min

Ph

\aI’ O-l/ ()/\\ w-h7

83%

siMe3

J.&; Colbert,J.C. Tetrahedron

I I J

k

* d

Kunishima,M.; Hi&i, K.; Tani, S,; Kato, A. Tetrahedron

Ph

76%

Lett., 1994, 35, 7253

8%(PCy3)g1,Ru=CHCH=CPh2 PhH ,55”C, 3h

Miller, S.J.; Kim, S.-H.; Chen,Z.-R.; Grubbs.R&J. Am. Chem. Sot., 1995, 117, 2108

Section 210

Alkenes from Misc.

225

(96.

4)

44%

W,; Schrisder, F. Tetrahedron Lett., 1994, 35,7935

B

Ni(dppe)Clz,iPrMgBr , THF Me$iCl , rt , (seconds)

Ma1 _

,; Urso,A.; Lardicci,L. Tetrahedron L&t., 2995, 36, 1133

Ar = 2,4-dibromophenyl 68%(97%ee) ; Calabrese, J.C. J. Am. Chem. Sot., 1995, 117, 8992 REVIEW:

“Reagent-Controlled AsymmetricDiels-AlderReactions,”Qh.T,; Reilly, M. Org. Prep. Proceed. Int., 1994, 26, 129

SECTION

r

210: 0 II 0888q pN \ t-Bu

ALKENES FROM COMPOUNDS

MISCELLANEOUS

1. BuLi , THF , -78OC 2. 4.C EtI1lH23C&Me 3. KOt-Bu

CllH23

-Y 5. CeC13,NaBH4 6. THF, 105OC,20h 63x%x93x92% (102:1 E.-Z) Denmark. S.E,; Amburgey,J. J. Am. Chem. Sot., 1993, 115, 10386

226


2% Pd(acac)z , BuLi , THF , reflux *

Section 210

vGoH21

70%

Gai, Y.; Jin, L.; Jnlia. M.: Verneaux. J.-N, J. Chem. Sot. Chem. Commun., 1993, BuLi

9 2%

1625

Wa~d3

O°C +

reflux

+

C3H7-C3H7 79% (76:24 E.-Z)

Jin, L.; Julia. M.; Verpeaux, J.N. Synlett, 1994, Ph-s-

215

KOH , Al203 , CBr2F+BuOH

Ph

t

Phm

02

Ph

96% (Ihan. T.-L,; Fang, SF.; Li, Y.; Man, T.-O.; Poon, C.-D. J. Chem. Sot. Chem. Commun., 1994, 1771

Ph

02Ph

4

8 eq. SmI2, THF , DMPU 35 min

*

PhwPh

95% Ph Keck. Cr.E,; Savin, K.A.; Weglarz, M.A. J. Org. Chem., 1995, 60, 3194

OEt s6 II

Shimagaki.

.OEt

(E:Z 9:l)

Lawesson’s reagent, xylene *

reflux ,22h

CgH1gwC$117

quant. Lett., 1995, 36 719

0 M,; Fujieda, Y.; Kimura, T.; Makata, T. Tetrahedron Mg” , cat. HgC12, EtOH SO2Ph

5 rt ,2h

Lee, G.H.; Lee, H.K.; Choi, E.B.; Kim, B.T.; Pak, cI.S, Tetrahedron REVIEW: “Rare Earth Metal Trifluoromethanesulfonates as Water-Tolerated Organic Synthesis,” Kobavashi. S, Synlett, 1994, 679

Let?., 1995,

98% 36,

5607

Lewis Acid CatIaysts in


Oxides from Alcohols

Section 213

CHAPTER

227

15

PREPARATION

OF OXIDES

This chapter contains reactions which prepare the oxides of nitrogen, sulfur and selenium. Included are N-oxides, nitroso and nitro compounds, nitrile oxides, sulfoxides, selenoxides and sulfones. Oximes are considered to be amines and appear in those sections. Preparation of sulfonic acid derivatives are found in Chapter Two and the preparation of sulfonates in Chapter Ten.

SECTION

211: OXIDES

FROM

ALKYNES

1. ClPPh2 , NEt3 , THF , -78°C

-coMe

; Slattery, B.J. Tetrahedror~~k~.,1994, 35, 5137

SECTION

212: OXIDES

\ 0 I

FROM

ACID DERIVATIVES SnMe3

SO2Cl Me

*

PhCl, 130°C

/

Me

2d

Neumann.W.P,; Wicemec,C. Chem. Ber., 1993, 126, 763

SECTION

213: OXIDES

FROM

ALCOHOLS

>(

0

I , -40°c 0 CH2C12 2. air

AND THIOLS

1. -S-l Gu, D.; m

IIN, Tetrahedron

Lett., 1993, 34, 67

-so$-I

74%

228

Compendium

SECTION

214: OXIDES


FROM

ALDEHYDES

NO ADDITIONAL

SECTION

215:

OXIDES ARYLS

FROM

EXAMPLES

ALKYLS,

NO ADDITIONAL

SECTION

216: OXIDES

FROM

217: OXIDES

Ph-

NI OH

Ph

FROM

METHYLENES

AND

EXAMPLES

AMIDES

NO ADDITIONAL

SECTION

Section 219

EXAMPLES

AMINES

0,05 Pr4N Ru04 , 1.5 NM0

b

Ph*?-

Ph I %

MeCN,rt,2d

75% (>50:1 ZE) Goti. A,; De Sarlo, F.; Romani, M. Tetrahedron

L&t., 1994, 35, 6571

H2N-(=)-co2H ,““” * Webb. K&;

Seneviratne, V. Tetrahedron

Lett., 1995, 36, 2377

SECTION

218: OXIDES

ESTERS

FROM

Na$02Tol, THF 0.01 Pd(PPh3)4, rt i)Ac

chiral phosphine ,72h

S02Tol

..

(10 Eichelmann,

H.; M.

SECTION

219:

H.-J, Tetrahedron

OXIDES FROM THIOETHERS

S

Guertin, K.R.; -de.

L&

OS(=O)Tol 1) 83%

Asymmetry, 1995, 6, 643

ETHERS,

5% TPAP ,3 eq. NM0 MeCN , 30°C, 4A MS ,2h 0

+T

EPOXIDES

w

TPAP = (n-Pr)fl Ru04 Tetrahedron Lett., 1993, 34, 5369

AND

92%

Section 219

Oxides from Ethers

WW4,

229

hv (Pyrex)

7I

PhHsAMe PhHsL

CH2Q

Me

92% Ramkumar, D.; $3.nkararaman. S, Synthesis,

1057 ?I

H202, MeCN , K2C03

PhHS-Me Page. PC&,

1993,

PhHs-

Me 82% MeOH, O°C ,2h Graham, A.E.; Bethell, D.; Park, B.K. Synth. Commun., 1993, 23, 1507 Mn02, Me3SiC1, MeOH

Ph--‘,Me

0 II 99% S ’ Me 23, 1759

w Ph.

Bell&a, F.; Ghelfi. F,; Pagnoni, U.M.; Pinetti, A. Synth. Commun., t-BuOOH, H20, 70°C, 30min BuHS,

*

Bu

1993,

0 II

B/N Bu J+inmelli. F,; Pellegrino,R.; Pizzo, F. Synth. Commun., 1993, 23, 3157

quant.

0

cyclohexanone monooxygenase w

Ph?*

II Ph/‘*

73%(99%ee, R) Secundo,F.; Carrea.G,; Dallavalle,S.; Franzosi,G. Tetrahedron Asymmetry, 1993, 4, 1981 1.35eq.oxone * rt, 1.2h with 0.65eq.Oxone- obtain47%sulfoxide We&J&

Tetrahedron

Lett., 1994, l

‘44

1.1

83%

35, 3457

P

$3F3

.N \ + F

0

II 95% CHC13, CFC13, -40°C ph\/s\ with 2.7 eq.,obtainthe sulfone(91%) DesMarteau.D.D,; Petrov, V.A.; Montanaari,V.; Pregnolato,M.; Resnati.G, J. Org. Chem., 1994, 59, 2762

ph\/s\

C4F9

*

230

Compendium


NaI04, cat. RuC13eH20 Ph-‘-

Ph

Su. W. Tetrahedron

Section 219

0

/

0

NH Ph-S-Ph

lh Lett., 1994, 35, 4955

quant.

NHAc &

mcpba

*

NHAc

xfx

+x)c

C

.

(8 Glass. R&; Singh, W.P.; Hay, B.A. Tetrahedron

1. Ph\/SIMe

I

3)

Lett., 1994, 35, kO9

H202, ether, DBU , -28OC (-)-camphorsulfonylimine 1

2. aq. Na sulfite Me. P.CB,; Heer, .J.P.; Bethell, D.; Collington, 1994, 35, 9629

quant (35% ee, R) E.W.; Andrews, D.M. Tetrahedron Lett.,

NaOCl , TEMPO,

Ph”,

Me

Bu@Cl , CH#X2,

KBr

0 II

* PhHs,

satd. NaHCO3

Me

87% Siedlecka, R.; Skarzewski.

J, Synthesis, 1994, 401 0 II

PhIO , cat. TsOH , MeCN ,25OC *

Ph/‘\Me . . avlca

.

82%

Ph/‘\Me G, Synth. Commun., 1994, 24, 2223 1. Mn02-35% aq. HCl , MeOH 0°C + 10°C, 0.75h

Pl?

0 II

t

Me

99%

2. NaOH Ph/‘lMe Fabretti, A.; Ghelfi, F.; Grandi. R,; Pagnoni, U.M. Synth. Commun., 1994, 24, 2393 NaBQ Ph /‘-Me

, II, wet zeolite F-9

0 w

II

CH2C12, lh PhRSNMe Hirano, M.; Kudo, H.; rvl[orimoto. T, Bull. Chem. Sot. Jpn., 1994, 67, 1492

82%

Section 219

Oxides from Ethers

231

PhIO , MeCN , lh 10% Mn salen catalyst

Ph-‘lMe

0 II ‘-Me

PF

57% (62% ee, R) Noda,K.; Hosoya,N.; Irie, R.; Yamashita,Y.; J(atsuki.T, Tetrahedron, 1994, 50, 9609

p-Tel/

‘+Me

0 II HS-Me p-To1

chiraloxaziridine, CHg12 t o”c

70% ee W .B,; Kochanewyczm,M.J.; Lovely, C.J.; Boyd, D.R. J. Chem. Sot. Chem. Commun., 1994, 25 69

PhMezCOOH, Ti(OiPr)d, Hz0 PhjSIMe

77% (99% ee,R)

II

*

S

(RR)-DET, CH2C12,-2OOC Ph’ ‘Me Brunel,J.-M.; Diter, P.; Duetsch,M.; Kag;ln. HB, J. Org. Chem., 1995, 60, 8086 1.5M HNO3,1% FeBq ,30 min

0 II

*

B+Bu

84%

B/\Bu Sutiez, A.R.; Rossi,L.I.; Martin, S.E. Tetrahedron Lett., 1995, 36, 1201

B4s\

SiO2, CH2C12,t-B&OH > Bu 30min

0

II S Bu’ ‘Bu

86%

with 2 eq. t-B&OH, obtain83%of sulfone P.J, Tetrahedron Lett., 1995, 36, 3825 Breton,G.W.; Fields,J.D.; m. cyclohexanone monooxygenase *

PhAS’

Pasta.P,; Carrea,G.; Holland,H.L.; Dallavalle,S. Tetrahedron

PhHs,

Me

Nagata,T.; -K.;

Ph-S’ II

0 97% (54% ee, R) Asymmetry, 1995, 6, 933

0

02 , m-xylene, Mn (III) salencomplex t

II

66%(51%ee) t-BuCHO, rt Me Yamada,T.; Mukaiyama,T. Butt. Chem. Sot. Jpn., 1995, 68, 3241 Ph”,

232


SECTION

220: OXIDES

FROM

HALIDES

Section 222

AND SULFONATES

Phi , CuI , DMF , heat PhS02Na Suzuki. H,; Abe, H. Tetrahedron Lett.,

SECTION

221: OXIDES

a 1995,

FROM

36,

PhSO$‘h

6239

HYDRIDES

NO2-03, CH2C12 *

Me -1OOC ,3h

a; M. From

. . .

51%(57:2:41o:m:p) Murashima,T.; Kozai, I.; Mori, T. J. Chem. Sot., Perkin Trans. I., 1993, 1591 It; Mori, T. J. Chem. Sot., Perkin Trans. I., 1995, 29 1 aryl

Suzuki.; From

.

aryl

Suzuki.;

esters:

meta-nitro

is the

major

product

Tomaru,J.-i.; Murashima,T. J. Chem. Sot., Perkin Trans. I., 1994, 2413 acetates:

ortho:para

predominates

(60:40)

Tatsumi,A.; Ishibashi,T.; Mori, T. J. Chem. Sot., Perkin Trans. l., 1995, 339 NO2-03, MeCN, MgO , O°C

R = Et R=H

95% (14:31:55 0:m:p) 0% . &&,l, H; Yonezawa,S.; Mori, T. Bull. Chem. Sot. Jpn., 1995, 68, 1535 REVIEW:

“Ozone-MediatedNitrationof AromaticCompounds with LowerOxidesof Nitrogen,”Mori, T.; &z&i. K Synlett, 1995, 383

SECTION

222: OXIDES

J5 Olah, GA.;

0

FROM

KETONES

1. NH20H, PtCl , KOH NO2

2. CF3C03H

(1113exo:endo) Ramaiah,P.; P&ash. CKS, J. Org. Chem., 1993, 58, 763

60%

Section 225

SECTION

Oxides from Misc.

223: OXIDES

FROM

233

NITRILES

hv (254 nm) SO2Ph Li, C.; Fuchs. P.L Tetrahedron

SECTION

224: OXIDES

55%

MeCN ,25,C, 2h Lett., 1993, 34, 1855

FROM

ALKENES

Et*\ 0-N& EtO’\, 0

9 Bu$nH

toluene, AIBN (syringepump)

mBu

EtO\ -Bu EtO-[, 0

Balczewski,P.; MikoIajczyk, M. Synthesis, 1995, 392

SECTION

225:

OXIDES FROM COMPOUNDS

72%

MISCELLANEOUS

PhMgBr, THF ,25OC

*

71%

i?h Cardellicchio,C.; Fiandanese, V.; Naso.F,; Pietrusiewicz,KM.; WSewski,W. Tetrahedron Lett., 1993, 34, 3135

PhCHO t cDc13

Oe5M

Me2N

t-Bu + Me2N

Denmark.SE,; Griedel,B.D.; Coe,D.M. J. Org. Chem., 1993,*58, 988

t-Bu

234


PhO#

Ph

7

Section 225

S02Ph 1. LiNAPH

2.

Br-

. . Yu, J.; Cho, H.-S.; Chandrasekhar, S.; Falck. J.R... Mlmkours)sl. (1, Tetrahedron 35,5437

Lett., 1994,

0

0 THF,l-t

Cardellicchio, C.; Fiandanese, V.; mo. Tetrahedron Lett., 1994, 35, 6343

F,; Pacifico, S.; Koprowski,

61% (>98% ee, S) M.; &&u.&wicz. K.M.


Section 302

AIkyne - Alcohol

CHAPTER

235

16

PREPARATION COMPOUNDS

OF DIFUNCTIONAL

SECTION 300: ALKYNE - ALKYNE 1. NaNTMS2 ; NBS ~~~‘~~~~-Bu

Maeriotis. P.pL; Vourloumis, D.; Scott, M.E.; Tarli, A. Tetrahedron L&t., 199;, 34, 2071

SECTION 301: ALKYNE - ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 302: ALKYNE - ALCOHOL, THIOL

vCHO Brown.;

Lo-\ 1. Bu$nI , -85OC+ 2.3 eq. ZnC12

MsO

82%

ether, 25OC, 15 min 2. H202, NaOH Khire, U.R.; Racherla,U.S. Tetrahedron Lett., 1993,34,15 % +9 %

O°C

3.iPqCHO -*

OH

-

Bu 89% (98:2 antisyn)

Katsuhira, T.; Barada. T,; Maejima, K.; Osada,A.; Qku. A, J. Org. Chem., 1993, S&6166


236

Section 302

.

(94

6) 80% Zhang, L-T.; MO, X-S.; Huang, J-L.; Huang. Y.-Z< Tetrahedro;r Lat., 1993, 34, 1621 00

0, 0

1.2 eq. LDA, THF, -1OOOC 2.2 eq. PhCHO , THJ?

p-To Y

3. NaH ,THF , O°C

I z

H

siAk3

Kusuda, S.; Kawamura, K.; Ueno, Y.; Toru.

0

Ph 83% (>99%ee, S) Tetrahedron Let?., 1993, 34, 6587

1.3 eq. t-BuLi 2. EtCHO , -78OC +

II Ph.

-3OOC *

k Ph Cl Satoh, T.; Hayashi, Y.; Yamakawa.

;>ePh 67%

Bull. Chem. Sot. Jpn., 1993, 66, 1866

1. o-DCB , reflux

w

2. TBAF

Jin, J.; Smith, D.T.; weimb.

SK

J. Org. Chem., 1995, 60, 5366

(PhCd&AlEt2’

Na+

PhCHO To1 , O°C , lh

)

Ph>ePh

OH Ahn, J.H.; Joung, M.J.; Yoon. N.M, J. Org. Chem., 1995, 60, 6173

95%

Bu-Bu C8HlY

I

SmI2, HMPA/PhH

Bu 78% Kunishima, M.; Tanaka, S.; Kono, K.; Hioki, K.; Tani, S, Tetrahedron Let?., 1995, 36, 3707

Alkyne - Amine

Section 305

237

t-BuCHO , Ga13, NEt3 Ph

=

H

-

Pl?

=

TfWfi 80% Han, Y.; Huanae. Y.-7, Tetrahedron L&t., 1995, 36, 7277 Ph

=

SnBu3

+

PhCHO

;>el’h

InC13 , MeCN ,25OC ,30 min 92% Yasu&, M.; Miyai, T.; Shibata, I.; Baba, A,; Nomura, R.; Mats&a, H. Tetrahedron Let?., 1995, 36,9497 PhCHO , Zn , THF

+ satd. NH&l,

Ph>

Phx

rt

.

(89 -I.;

Riazi-Kermani,

F. Synth. Commun., 1995, 2.5,

SECTION 303: ALKYNE SPh

2923

11) 68%

l

- ALDEHYDE 1. s02C12,

cc4, o”c

Fortes. CC;

+ PWCHO 2. CuC12, H@ Garrote, C.F.D. Synth. Commun., 1993, 23, 2869

SECTION

304: ALKYNE

47%

Ph---==----/

- AMIDE NO ADDITIONAL

EXAMPLES

SECTION 305: ALKYNE - AMINE 2 Et2NH2, 1% CuCl

-

(““”

THF , 50°C, 2h Imada, Y.; Yuasa, M.; Nakamura, I.; &&K&K&. F2B

WuJJ.-L;

=

.

NEt2

S.-L J. Org. Chem., 1994, 59, 2282

SiMe3

/

OH

Yan, D.-S.; Tsai, H.-W.; Chen, S.-H. Tetrahedron Let?., 1994, 35, 5003

91%

238


BuNH2,3%

gBr

Section 307

CuBr , MeCN b

90%

Geri, R.; Polizzi, C.; Lardicci, L.; Qporusso. A.m Gazz. Chim. Ital., 1994, 124, 241

Okita, T.; hobe. M, Tetrahedron, 1995, 51, 3737

SECTION

306: ALKYNE

- ESTER NO ADDITIONAL

SECTION

Phu

307: ALKYNE

- ETHER,

EXAMPLES

EPOXIDE,

THIOETHER

!-c) PhSeSePh L

* Ph- CZC-SePh 75% CuI , HMPA Reckziegel, A.; Menezes, P.H.; Stefani, H.A. Tetrahedron Let?., 1993, 34, 393

=C-Br &;

PhSeBr , CuI , DMF W-4

a

-H

C5H,lpSPh

82% Silveira, C.C.; Reckziegel, A.; Menezes, P.H. Tetrahedron Let?., 1993, 34, 8041

Braga. a;

PhI(OAc)2, PhSeSePh , CH2C12 Ph

w

=

Ph

=

SePh

4o”c 81%

Tingoli, M,; Tiecco, M.; Testaferri, L.; Balducci, R. Synlett, 1993, 211

\ 0I / HO

OCOCF3

, MeCN

DBU , CuC12e2H20 , O°C

0

// 4

83% Godfrev U-D,; Mueller, R.H.; Sedergran, T.C.; Soundararajan, N.; Colandrea, V.J. Tetrahedron Let?., 1994, 35, 6405

Section 311

SECTION

Alkyne - Alkene

308: ALKYNE

239

- HALIDE

k:

1;;

&&velm

V,; Rollin, Y.; G&&henne, C.; Gosmini, C.; P&ichon, J. Tetrahedron L&t.,

1994, 35, 4777

(collidine)$

P-H Brunel, Y.; JXouw. SECTION

PF6

t

Ph

=

I

75%

G, Tetrahedron Lett., 1995, 36, 2619

309: ALKYNE

- KETONE

J-c Cl

‘*

Ph

0

7NW *

2. FVP (5OO*C) ~R.A.;

PlPh

72% x 82%

H&ion, H.; Janosi, A.; Raut, S.V.; Seth, S.; Shannon, I.J.; Smith, F.C.


SECTION

310: ALKYNE

- NITRILE

1. CuCN , TMSCl , H20 DMSO , MeCN ,72h P-H

t

2. cat. NaI , 50°C uo. F.-T%;Wang, R.-T. Tetrahedron Lett., 1993, 34, 5911

SECTION

311: ALKYNE 2

P-CN

72%

- ALKENE 10% Pd(OAc)2, 30% PPh3 THF , reflux , lh

% &Iandai. T,; Tsujiguchi, Y.; Matsuoka, S. Tetrahedron Lett., 1993, 34, 7615

96%


240

Section 311

co Et

SiMe3

2

Pd(dba)z, Ph3As NMepyrrolidone , 40°C

OTf

90%

2, aq. HCl B.H,; Alami, M. Tetrahedron Lett., 1993, 34, 1433

mhutz.

0.05 Pd(PPh)4, 0.1 CuI 2eq.N&,PhH,lh Gueugnot, S.; Linstrumelle, G. Tetrahedron Lett., 1993, 34, 3853

w-h

-

1 5

.

Alaml.;

I

/--OH

c5

11

, Pd(PPh3)4,15min

0

-

M Ferri, F.; m.

*

H

\ 93%

G, Tetrahedron Lett., 1993, 34, 6403

1. norbomadiene, Bu3Sn = Ph 1% PdC12(PPh3)2,80-100°C, 20h Phi 2. heat

Ph

Kosuni. M,; Kimura, T.; Oda, H.; Migita, T. Bull. Chem. Sot. Jpn., 1993, 66, 3522 1. Cfl 11, Pd(PPh3)4, CuI

A

Cl a;

.

Cl

2. PdC12(PhCN)z,piperidine rt

Crousse,B.; Linstrumelle, G. Tetrahedron Lett., 1994, 35, 3543

phtph n. It&;

FVP (500°C)

-

Boeters, C.; Morrison, J.J. J. Chem. Sot., Perkin Trans. l., 1994, 2473

59%

Section 314

Acid - Aldehyde

SiMe3

C

241

Me3Si 1. set-BuLi , THF , -45OC 2.ZnBr2 -45OC + 20°C

SW3

s

3. H30+ SiMe3

-8-

85%

I... Nonnant. J.-F,; Platzer, N. Tetrahedron Lett., 1994, 35, 5645

Meyer, C.; u

Ph Ph 5% HRh(CO)(PPh3)3 35% PEt3 Bu

Z

H+ THF , reflux ,9h 68% (>20: 1 endo:exo)

\

Yamzguchi. M,; Omata, K.; Hirama, M. Tetrahedron Lett., 1994, 35, 5689

Ph

x

SnBu3

, Dibal , THF

YCl

Ni(acac)z , P(OEt)3 yrefiux 77% Cui, D.-M.; Hashimoto, N.; Ikeda. S,; Sato, Y. J. Org. Chem., 1995, 60, 5752

SECTION 312: CARBOXYLIC

ACID - CARBOXYLIC

NO ADDITIONAL


ACID

EXAMPLES

ACID - ALCOHOL,

THIOL

1.1:3 TiCldLiAlH4, lh CFC13 , THF , -5°C 2. aq. HCl 62% Garcia, M.; de1 Campo, C.; Sinisterra, J.V.; Llama, E.F, Tetrahedron Lett., 1993, 34, 7973


ACID - ALDEHYDE

NO ADDITIONAL

EXAMPLES

242



Section 316

ACID - AMIDE

Me M&J4

44,

1.2.2 LDA , ZnC12 2. HJO+

0/ A 0 T

.

a.

9

*

FY

N w-r

0

H

cog-I 86% (88% de)

U+; Maier, S. J. Chem. Sot. Chem. Commun., 1995, 199 1

5 eq. LDA ,2.5 eq. Al(OiPr)3

0

70% (98% ds/86% ee) J(azmaier. ‘IJ,; Krebs, A. Angew. Chem. Int. Ed. Engl., 1995, 34, 2012


0

A?--

ACID - AMINE

1. PhMgBr , THF , -40°C 2. TFA , CH2C12

C02Et

I BoC

3. DDQ , CH2C12 4.10% NaOH , reflux

C02H

-l+’ H

83~72~93% UJ.; Pedregal, C.; Rubio, A.; Valenciano, J.; Navio, J.L.G.; Alvarez-Builla, J.; Vaauero. u Tetrahedron Lett., 1993, 34, 6317

1. Ph//““”

w

OSiMe3

NHPh OSiMq

, ZnBr2, CH2C12 C02H

2. H30+ 84% (35:65 syn:anti)

]Mladenova. M,; Bellassoued, M. Synth. Commun., 1993, 23, 725

Section 318

Acid - Ether

243

Nc /“@Me~~~~h~~~~ep) (02H+ ‘“) (02H derivative, 25OC,40h 2.6N HCl

(94 T, Tetrahedron Lett., 1994, 35, 2713

Soloshonok, V.A.; m.

HO

NH2

Ho

NH2

.

6)

l

CO2H 1, oxaIy1chloride , ether 2. satd.NaHC03, refIux 3. TsNHNH2 , reflux 4. NaE3H4,THF

H

98x39% H

Guan, X.; Borcb=irdt,

Tetrahedron Lett., 1994, 35,3013

*

REVIEWS:

“RecentDevelopmentsin the StereoselectiveSynthesisof a-Amino Acids,” b&&r.

R-Q,

Tetrahedron, 1994,50, 1539

“RecentStereoselectiveSynthetic Approachesto P-Amino Acids,” Cole. IX,

Tetrahedron,

1994,50,9517

Section315 (Carboxylic Acid - Amide). Section344 (Amide - Ester). Section 351 (Amine - Ester).

RelatedMethods:


ACID - ESTER


SECTION 318:

CARBOXYLIC THIOETHER

ACID - ETHER, EPOXIDE,

C02H ..

(85 1 0 Mead. K.T; Pi&& SK. Tetrahedron Let?., 1993, 34, 6997

C02H 15)

82%

244

Section 322


SECTION 319: CARBOXYLIC OzH

b \

ACID - HALIDE, SULFONATE

1.2.2 eq. see-BuLiKMEDA THF , -9OOC 2.4 eq. c13cc13 , THF , -78OC

3.4N HCl / F Moyroud, J.; Guesnet,J.-L.; Bennetau,B.; Mortier. J I


ACID - KETONE 98% (>98% ee)

Na , n-C3H70H, reflux

Moody, H.M.; Kantein. B,; Broxterman,Q.B.; Boesten,W.H.J.; Kamphuis, J. Tetrahedron Lett., 1994, 35, 1777 0.5 C~(ClO4)24 Hz0 02, MeCN ,rt ,lO-15h **OH 0 &sy.

96%

J,; Belotti, D.; Bellosta, V.; Brocca, D. Tetrahedron Lett., 1994, 35, 6089 Also via: Section 360 (Ketone - Ester).


ACID - NITRILE

NO ADDITIONAL EXAMPLES Also via:

Section 361 (Nitrile - Ester).


ACID - ALKENE

1. CFz=CHLi 2. H30+

NC”

3 H O+ l

3

* *c02H

Tellier. F,; Sauvetre,R. Tetrahedron Lett., 1993, 34, 5433

60% (E)

245

Alcohol - Alcohol

Section 323

0.1 pcy3

,3 TESCI

zs g;*

lbkC~

A/ c3*&,’

c3H--J@902H

Hanamoto, T.; Baba, Y .; Inanaga. J, J. Org. Chem., 1993, 58, 299

=o=’

MnZnBr’ether

;F

Duchsne. A; Abarbi, M.; Pamin, J.-L.; Kitamura, M.;

,!402H Noy~ri,

R. Synlett, 1994, 524

Section 313 (Alcohol - Carboxylic Acids). Section349 (Amide - Alkene). Section 362 (Ester- Alkene). Section 376 (Nitrile - Alkene).

Also via:

SECTION 323: ALCOHOL, THIOL - ALCOHOL,

PhCHO ,SmI2,*

ph%ph

+

THIOL

phhcHo OH 1%

97% in THF + 2.8 eq. HMPA 10% Shiue, J-S.; Lin, C-C.; J%ng. J-M, Tetrahedron Lett., 1993, 34, 335 ~3W~N)6

Bu

9 K2C03

Bu

t-BuOH , H20,12h

r

N 6

~J.A,;

60%

OH 89%

ODHQ

SiMe3

.

80%

) 9 OS04

HOK

SiMe3 (89% ee)

DHQ = dihydroquinidine ODHQ

Rane, A.M.; L6pez, C.J. Tetrahedron Lett., 1993, 34, 1893 AD-mix-P

phoN

-t-BuOH , H20, 0°C PhO&OH 95% Tetrahedron Lett., 1993, 34, 2267 Wang, Z-M.; Zhang, X-L.; SharPless.

246

Section 323


Me

Me Rh+2 cat. , Cs2CO3 , PhBr

OH Barrett. A.G.w; Itoh, T.; Wallace, E.M. Tetrahedron Mt., 1993, 34, 2233

2 Lebrun, A.; &my.

0

1.2 eq. SmBr2 2. Hz0

J-I,; Kagan.

90% Tetrahedron Lett., 1993, 34, 2311

DHQ-CLB Me3SmC$-i11

H

Me& 93%(71%ee,R) 6H Zargarian, D. Tetrahedron ktt., 1993, 34,

Okatnoto, S.; Tani, K.; &Q. F.: ~K.B.; 2509 1. Ph$iSH , NEt3, MeOH P

2. TBAF, AcOH

-,,i-lt/OH

+

..

(7 Brittain, J.; m.

pASH

1)

Y, Tetrahedron Lett., I993, 34, 3363 H20, 10 KBar , 60°C, Id *

QH E

93% (49% ee) Kotsuki. H,; Kataoka, M.; Nishizawa, H. Tetrahedron Lett., 1993, 34,4037 7

l%Os04,1%catalyst

catalyst = bis-dihydrquinolyl

Crispino, GA.; Jeong, K.-S.-; Kolb, H.C,; Wang, Z-M.; Chem., 1993, 58, 3785

derivative

87%

c

247

Alcohol - Alcohol

Section 323

H

OH

H 1.10% Cp$QCl;! , ether / 2.5 eq. EtMgCl ,25OC, 12h 3. 02,OK

Et

-cc-r

70% (98:2 syn:anti)

Hovevda. A.J&; Morken, J.P. J. Org. Chem., 1993, 58, 4237

,

1%OS04,l-t,3K2c&

OH

Oallyl

3 K3Fe(CN)6,3 MeSO$H2,

t-BuOH-Hz0 82% (39% ee, R) Am. Chem. Sot.,

Morikawa, K.; Park, J.; Andersson, P.G.; Hashiyama, T.; VJ. 1993, 115, 8463 1. Li powder, CH& 5% 4,4’-di-t-Bubiphenyl THF , -4OOC

CHO

H

H

2. H20 +Y

52%

Guijarro, A.; Yus. M, Tetrahedron Lett., 1994, 35, 253

(95

.

5)

93%

Adam. WJ Gevert, 0.; Klug, P. Tetrahedron L&t., 1994, 35, 1681 ’ OH AD-mix f3 , aq. t-BuOH , O°C phw

5r PhS

Ph

Walsh, P.J.; Ho, P.T.; King, S.B.; wss.

+ OH (98% ee, 2S,3R) K.B. Tetrahedron Lett., 1994, 35, 5129

Ph 75%

Section 323


248

+wph

+

*o/

Jph

955 synmi O (94% ee, syn)

21%

50% ee, S

H Kaneko, Y.; Matsuo, T.; I(,ivooka. S, Tetrahedron Lett., 1994, 35, 4107

Yb-TMS-Br

OTMS

)

fl!p

62%

THF-HMPA TMSO ; Nakahashi, M.; Kuno, T.; Tsuno, M.; Makioka, Y.; I&&i. Tetrahedron Lett., 1994, 35,411l .

.

K.: Fujiwam Y,

0 t-BUSH, hv

)

K

C6H13U

Me

57% (4:l syn:anti) Newcomb. M,; Dhanabalasingam, B. Tetrahedron Lett., 1994, 35, 5193 Ph

0.1 Kz0~04 ,3 MeSOflH2

K3k(cN)6

,3 K2C03

OH

O°C , 12h

R = cinchonidine Corey. EJ.; Noe, M.C.; Grogan, M.J. Tetrahedron Lett., 1994, 35, 6405 NbC13, THF , rt 2 t-BuCHO

t

71% (>95:5 d,l:meso) zvmoniak. J,; Besangon, J.; MoIse, C. Tetrahedron, 1994, 50, 2841

Alcohol - Alcohol

Section 323

Al,KOH,MeOH,rt,5min

+

PhCHO

249

87% (1:l d,l:meso)

Ph Ph

OH Khurana. J.M,; SehgaI, A. J. Chem. Sot. Chem. Commun., 1994, 571 1. dIpczBH , ether , -78OC 2. PhCHO , -78OC *

3. NaOH , Hz02

PhL

= = AH

76% (>95% ee)

Brown. H.C,; Narla, G. .J. Org. Chem., 1995, 60, 4686 P$

*n l

&N,

H

Ph

Ph/

+

Ph e

H

/O

B

Ph

H

* BH3, THF

0

Ph 3 OH (16% meso:RR+SS (99% ee SS)

Quallich. G.J,; Keavey, K.N.; WoodaIl, T.M. Tetrahedron Lett., 1995, 36, 4729 CHO

C

CHO

Bu$nH , PhH ,2O”C hv

ta

OH OH

46% (98: 1 cixtrans)

Hays, D.S.; Fu. G.C, J. Am. Chem. Sot., 1995, 117, 7283 Ph

es 9 t-BuOH , H20, &Fe(CN)e

* Ph K2CO3, (DHQDhPHAL , K~OSO~)OH)~

OH 95% (97% ee , R)

Torii, S.; Liu, P.; Tanaka, H. Chem. Lett., 1995, 319 REVIEWS:

“Synthesis of cr.,@-Alkenediols.A Review,” Patwardhan.S.A, Org. Prep. Proceed. Ink, 1994, 26, 645

Section 325


250

“The Oxygenation of Vinyl Cyclopropanesas an Entry Into Stereoselective1,3-Diol Synthesis,” Feldman. Synlett, 1995, 2 17 “Catalytic Asymmetric Dihydroxylation,” Kolb, H.C.; Van Nieuwenhze, M.S.; SharPless. K.B. Chem. Rev., 1994, 94,, 2483

Also via:

Section 327 (Alcohol - Ester).

SECTION 324: ALCOHOL,

Section 357 (Ester - Ester).

THIOL - ALDEHYDE

1. PhCHO , NEt3 *

II-CHO

+)-cO2H

2. H30+ I

51% Barco, A.; Benetti, S.; De Risi, C.; Pollini, G.P.; Spalluto, G.; Zanirato, V. Tetrahedron Lett., zp

34, 3907

1993,

[RhCI(CO)& , 1-methylpyrazoIe HSiMe2Ph , CO (50 atm) Fukumoto, Y.; Chatani, N.; Murai. S, J. Org. Chem., 1993, 58, 4187 0

9vp)c cs /“7\

Ph$=CHOMe , CHCl3,2X

*

CHO

C6H13

Yu, L.; u

C6H13

QH s = = -CHO

77%

ZAJ. Chem. Sot. Chem. Commun., 1993, 232

Section 330 (Alcohol - Ketone).

RelatedMethods:


mo2

NA Cl

THIOL - AMIDE

1. EtCHO , Li(powder) 3% C1()Hg,THF 2. H20 *

m-92N

w

71% OH

Ram6n, D.J.; Yus. M, Tetrahedron Lett., 1993, 34, 7115 NHTs 3

m.

aq.NaOH, 100°E (-h

.

J,; Bats, J-P.; Hautefaye,P.; Nuhrich, A.; Lamidey, A-M.


,o~5%

Section 325

Alcohol - Amide

251

H

MeS02NH2, t-BuOH , Hz0 rt , AD-mix-pTM *

mt

Ph

2

96% (96% ee)

v

mt2

OH AD-mix-pm= 5% DHQDz-PHAL (chichona alkaloid-phthalzine reagent),2% K~OSO~(OH)~ Bennani, Y.L.; -less. KB, Tetrahedron Lett., 1993, 34, 2079 COzMe

1. Dibal , -78OC 2.

NHCbz

OTMS

H OMe 3. TiCl2(OiPr)z

.

H

*A

CO&k

= = = I

+

NHCbz

CO2Me

2s

66%

10%

K yooka. S.; Suzuki, K.; Shirouchi, M.; Kaneko, Y.; Tanimori, S. Tetrahedron Lett., 1993, 34, 5;29

HO Me2CuLi , Me (96 Reetz. M.T,; Riilfing, K.; Griebenow, N. Tetrahedron Lett., 1994, j5, 1969

1. BuLi , -78°C 2. LiNaphth , -78°C

pBz

3. PhCHO

me2

FHBz

p +

(1 Foubelo, F.; Yus.

4)

84%

OH

!Ph

..

1) 72%


1. LDA , THF , -78°C 2. CeC13,THF , rt

* PhnfMe2 3. PhCHO , THF , -78OC 0 OH Shang, X.; Liu. H.-J,Synth. Commun., 1994, 24, 2485

0

68%

. H 3) 66% (97 Taniguchi, M.; Fujii, H.; Oshima. K.: Utimoto, K, Bull. Chem. SO;. Jpn., 1994, 67, 2514

252


Section 326

hv

Nfw-b3

-G

c

0 HO

jJ

86%

0 w-h3 Dlttarm., Xu, F.; Qi, H.; Martin, M.W.; Bordner, J.; Decosta,D.L.; Kiplinger, J.; Reiche, P.; Ware, R. Tetrahedron Lett., 1995, 36, 4197 .

.

CL

(CHzO), , acetone, K2CO3 ) ON 0 N 0 N H20, ultrasound I H d OH Jouglet, B.; Oumoch, S.; Rosseau.G, Synth. Commun., 1995, 25, 3869


B

O@

96%

THIOL - AMINE

1. LDA , TiC12(OiPr)2 THF * 2. t-BuCHO , THF 3. H30+

Et02C&ph

+

Et02Aph

6H

Ph

(>99

OH :

1)

78%

jf

KanemasaI S,; Mori, T.; Wada, E.; Tatsukawa,A. Tetrahedron Lett., 1993, 34,677 OH Ph Ph

2 TsNCO , THF , Id 2% Pd[P(OiPr)&

reflux OH

Xu, D.; -less.

K.B Tetrahedron Lett., 1993, 34, 951

l- WSiMq

, SnC14

CH2C12,O°C,30 min 2.TBAF,m

(1.

.

Hioki. H,; Okauda,M.; Miyagi, W.; It& S. Tetrahedron Lett., 1993, 34, 6131

1.1) 74%

253

Alcohol - Amine

Section 326

Keck. G&, PaIani, A. Tetrahedrdn Lett., 1993, 34, 3223 H

4r H

5 eq. TABH , AcOH/MeCN Me

Me

P

-35OC +

P &

+22”C

* NHOBn TABH = Me+JH BH(OAc)3 Osterhout, M.H.; Reddy, J.P. Tetrahedron Lett., 1993, 34, 3271 N-OBn

DA;

Ph-

Br

2 eq. SmI2, THF-HMPA CHO t N=C , -15OC, 3h

91%

Murakami, M.; Kawano, T.; Ito, H.; Ito. Y, J. Org. Chem., 1993, 58, 1458

0

H 1. LDA 2. PhCHO

+

Ph

*

mn2

Lagu, B.R.; Crane, H.M.; m.

*

NBn2

(80:20, R)

D.C, J. Org. Chem., 1993, 58, 4191 EtzNzCu(CN)Liz , THF

0 -78OC + rt

N. Y,; Asao, N.; Meguro, M.; Tsukuda, N.; Nemoto, H.; Sadayori, N.; Wilson, J.G.; Nakamura, H. .I. Chem. Sot. Chem. Commun., 1993, 1201

254


Section 326

Yb(OTf)3, NHEt2 CH&

C6H13

97%

,20 min mt2

w-h3

> 99% a-attack Chini, M.; Crotti, P.; Favero, L.; Macchia, F.; Pineschi, M. Tetruhedrun Lett., 1994, 35,433 C8H

7

Et2NH , LiBF4, MeCN 80°C , 18h

* c8H1ym.YOH Chini, M.; Crotti. P,; Favero, L.; Macchia, F. Tetrahedron Lett., 1994, 35, 761 b

CbZ

0

CbZ

79) 52%

.

(21

&&,Q. T,; Tajiri, IS.; Harimoto, T.; Ninomiya, I.; Kiguchi, T. Tetrahedron Lett., 1994, X5,2205 H

H CH3N02 ,2 eq. AlC13 w 8O”C, 5h

\

/““” 70%

/

.

Sarton,;

Bigi, F.; Maggi, R.; Tomasini, F. Tetrahedron Lett., 1994, 35, 2393 Ph I N /\

1. Li, cat. cl(jf&j 2. PhCHO *

3. H20

Almena, J.; Foubelo, F.; Yus. MJ.

0 o=

68%

PhHN-Ph

various electrophiles were used Org. Chem., 1994, 59, 3210 93% (1:l)

MeCH=N-OMe , iPrOH

sono.

& /

* e’

NHOMe

T,; Kise, N.; Fujimoto, T.; Yamanami, A.; Nomura, R. J. Org. Chem., 1994, 59, 1730

Section 326

Alcohol - Amine

c”, f”’

1. BH#Me2,

255

c’)

THF

J

w

2. MeOH

45%

3. H202, NaOH w-h1

C&9

Goralski. CT%;Hasha,D.L.; Nicholson, L.W.; Zakett, D.; Fisher, G.B.; Singaram. B, Tetrahedron L&t., 1994, 35, 3251 0

A

2

H

Sm , Me$iCl/NaI , MeCN rt, 15min

P

-

9

/

OH

Phq-p 72%

Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y .; Ishii. Y cJ. Org. Chem., 1994, 59, 7902

NBn2

mn2

(92:8 RS)

90%

with LDA

(63:7 R:S) 90% Lagu, B.R.; Liotta. DC, Tetrahedron Lett., 1994, 35,4485

l.BMS,THF

J5 ~c.T.;

.

3. H202, NaOH

Hasha,D.L.; Nicholson, L.W.; Sine.

R, Tetrahedron Lett., 1994, 35, 5165

OH ultrasound,Al(Hg) , aq. THF 2h iJo Fitch, R.W.; Luzzio. F.A, Tetrahedron Lett., 1994, 35, 6013

92% NH2

Section 326


256

t-BuNH2 , CH2C12 5% Yb(OTf)3, rt ,16h c8H~~mt-Bi8H~~;Bu m

99 P,; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lejt., 1994, 35, 7089 Bn I

Bn I

1. Cp$Zr(Bu);!, THF -78OC+ rt ,4h OMe

2. BF3aEt2, THF , O°C 3. aq. NaOH

82% (>98:2 syn:anti)

Ito, H.; Ikeuchi, Y.; Taeuchi. T,; Hanzawa, Y.; Shiro, M. J. Am. Chem. Sot., 1994, 116, 5469 Na,iPrOH,THF

76% (erythro/threo = 0.8)

Bartoli, G.; Cimarelli, C.; Palmieri. G, J. Chem. Sot., Perkin Trans. I., 1994, 537

A

, SmI2

Q+ \ ‘0I /

*

THP , HMPA

85%

Booth, SE.; Benneche,T.; Undheim. K, Tetrahedron, 1995, 51, 3665 Ph 0

NHPh

PhNH2 , TiC13, PhCHO THF/CH$12, Py , rt *

M-+

Clerici, A.; Clerici, L.; porta 0, Tetrahedron L&t., 1995, 36, 5955

9 % HO Ph

Ph 76%

Section 327

Alcohol - Ester

257

OH

BnNH2,lOkbar ,CH2C12

90% cat. Yb(OTf), , rt ,6d Meguro, M.; Asao, N.; mote.

030s=Nt-Bu , DME ,25OC Phw

Ph

NHBn

Y, J. Chem. Sot., Perkin Trans. I., 1994, 2597

quinuclidine , 36h

NH?-Bu

- Ph+ph

+ Phqph OH

OH

..

(97

3)

Rubinstein, H.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, 439 1. TFAA, CHg12 rt ,4h OH

2. K2CO3

95%

Fontenas,C.; Bejan, E.; Haddon, H.A.; Belavoine, G.G.A,Synth. Commun., 1995,25, 629

SECTION 327: ALCOHOL, OBn = =

THIOL - ESTER

t

=

CHO

CO2Me

3% LiC104, -30°C CHg12, 4h

OSiMe2cBu

..

(92 Reetz. M.T,; Fox, D.N.A. Tetrahedron Lett., 1993, 34, 1119

8)

>84%

EtOH , CO, NaBr , iPr2NEt

-I.;

Pd2(C4H7)& , maleic anhydride ‘) H*co2Et Maruyama, T.; Makuta, T.; Yamamoto. A. Tetrahedron Lett., 1993, 34, iI35

w

Me

PhCHO ,5% SmI2,5 min

Ph

CH2C12, -78OC -$< OTMS Van de Weghe, P.; Collin, J, Tetrahedron Lett., 1993, 34, 3881

C02Me OTMS

95%

258


/L

OH

Yeast, pet. ether, H20 C02Et

Section 327

*

rt, Id

AC02Et

58% (94%ee) Yeast = Saccharomyces cerevisiae Jayasinghe,L.Y.; Smallridge. A.J,; Trewhella, M.A. Tetrahedron L&t., 1993, 34, 3949 0

0

C02Me Mn(OAc)3@2Hz0

OH

+

A

Cu(OAc)pHzO

9%

78%

25OC

ix

-OH

OMe

Oshima, T.; Sodeoka,M.; Shibasaki,M. Tetrahedron L&t., 1993, 34, 8509 . ;co2Me

NHC02t-Bu

t-Buo2cJ

c

*

-t &Me$‘h w.

‘.~~ao~~;a~ 2.5% aq. HCl

0 i bH

0

J&; Zhang, J. J. Org. Chem., 1993, 58, 294 OSiMe3 I PhCHO

Ph

m12

C02Me

er. LB, .I. Org. Chem., 1993, 58, 2324 TMs

A

OMe

92%

p-MS

10% [Cp2Zr(Ot-Bu)THF][BPh4]

:=

C02Me

PTMS +

&CO$Ie I= Z s=

CH2C12, PhCHO , rt , lh -^(

..

(1.1

1)

95%

Hong, Y .; Norris, D.J.; Collins, S, J. Org. Chem., 1993, 58, 3591 1. LDA 2. Et2AlC1

OH

/\COzt-Bu *

56%

xx 2’ (84:16 syn:anti) m. S&; Fried, J.A.; Grassl, Y.N.; Marolewski, A.E.; Pelton, E.A.; Poel, T.-J.; Rezanka, D.S.; Whittaker, M.R. J. Org. Chem., 1993, 58, 7304 3* ‘s

Section 327

Alcohol - Ester

259

BrCH2C02Et, PhTeLiKeC13 C02Et ether, OOC +

rt 95%

Fukuzawa. S.-i; Hirai, K. J. Chem. Sot., Perkin Trans. I., 1993, 1963 oxido reductase from Geotrichum candidum

C02Et

QH 0 = E

C02Et

500 mM bis-TRIS-HCl 24h , NaDPH , ADH , glucose

93%

(>99% de; 92% ee) Kawai. Y,; Takanobe, K.; Tsujimoto, M.; Ohno, A. Tetrahedron Lett., 1994, 35, 147 PhCHO

+

I-(,, TBSO

~e/wI-MP ()pMp

CH2C12, -78’C

+ OTBS (6

PMP = p-methoxyphenyl

UOPMP &TBS 94) 95% 92%ee

..

Kobayashi. S,; Kawasuji, T. Tetrahedron Lett., 1994, 35, 3329 OH 3 eq. CH2=CHC02Me

COzMe

1.2 MgBr2 , CH2C12 O°C , lh 58% (> 20~1 endo:exo) Woo. SH, Tetrahedron Lett., 1994, 35, 3975 TMS

+

ooka. S,; Kido, Y.; Kaneko, Y. Tetrahedron Lett., 1994, 35, 5243

260


BnOCH$HO

Section 327

,5% binolTiC12

toluene , O°C ,2h . -K.;

81% (94% ee, R)

.

Matsukawa, S. J. Am. Chem. Sot., 1994, 116, 4077 0

CaMe

MeOH , Amberlyst-15 ,2Oh

96% 0 bd.

OH

* c c R.c; Selvapalam, N. Synth. Commun., 1994, 24, 2743 OHC I

I--

1

CO2iR

L = chiral imine ligand Hayashi, M.; Inoue, T.; C)euni. N, .I. Chem. Sot. Chem. Commun., 1994, 341

o=

Br\/co2Et

, THF ,2h

0

LVT, rt

*

(-pco2Et

LVT = low valent titanium 67% Aoyagi, Y.; Tanaka, W.; Ohta. A, J. Chem. Sot. Chem. Commun., 1994, 1225 1. BuLi , ether, -4OOC 2. PhCHO

2”

H w

P

3.03 , CH2C12, -78°C 4. Me$

Ph*CO

2 Me

51% Hormuth, S.; &i&&

H.-U.; Dorsch, D. Liebigs Ann. Chem., 1994, 121 RuBr&hiral

C02Me

mM.J.;

bis-phosphine)

60 psi H2 , aq. MeOH

*

OH = = z &COzMe

quant. (99% ee, S) Harper, T.G.P.; Kalberg, C.S. J. Am. Chem. Sot., 1995, 117, 4423

Section 328

Alcohol - Ether

261

0

VO(OAC)~ , PhH , TBHP -

A Ph

o/\/O” 98%

Choudary, B.M.; Reddy, P.N. Synlett, 1995,959 Also via:

Section 313 (Alcohol - Carboxylic Acid).

SECTION 328:

ALCOHOL, THIOL - ETHER, EPOXIDE, THIOETHER

E+Z

. 1) (18 Mandai. T,; Ueda, M.; Kashiwagi, K.; Kawada, M. Tetrahedron Lett.: 1993, 34, 111

0 0

Uozumi, Y.; w.

1. 0.1% [PdC1(rtC3H5)]2 0.2% R-MOP, HSiCl3

H RMOP b 65 x 83%

(g5% ee) T, Tetrahedron Lett., 1993, 34, 2335

1. BH#Me2, Me2S , O°C 2. aq. NaOH , Hz02 3. NaOH

mder.

=3 .

OMe

40°C, 24h 2. KF , KHC03, Hz02

78%

G,&; Bobbitt, K.L.t .I. Am. Chem. Sot., 1993, 11.5, 7517

pm2

Section 328


262

1. BuCHO , Li(powder) 5% DTBB , THF, O°C 2 H o

EtQc1

l

H Et

*

2

gK

87%

Bu

Guijarro, A.; yuS. n& Tetrahedron Lett., 1993, 34, 3487

‘-“’

cat BF3 OEt2 .

42%

l

Mark& I.E.; Bayston, D.J. Tetrahedron Lett., 1993, 34, 6595

phxph

n

2 eq. BHpSMe2 2 eq. TMSOTf

Bartels, B.; Hunter. R, J. Org. Chem., 1993, 58, 6756

7 PhSH , SiO2

;;;p

+ z&SPh

t

20°C, 20h

Me3Si

CdJ

13

89% Raubo, P.; w

C&

13

14%

a-h3

J, Synlett, 1993, 25 ClCH2SPh , SmI2 t

0

(-KS,,

o=

73% Yamashita, M.; Kitagawa, K.; Ohhara, T.; Iida, Y.; Masumi, A.; Kawasaki, I.; Ohta. S, Chem. Lett., 1993, 653

R

1. PhONa , DMF

A0

)

PhOTOBn

2. HCl-H20 k/

OBn

Cwlsen. P.H.J*; Aase, K. Acta Chem. Stand. B., 1993, 47, 617

OH 81%

Section 328

Alcohol - Ether

263

cat. FeC13, MeOH ,25OC

Ph

OH

0.75h

90%

N,; Salehi, P. Synthesis, 1994, 1152

a

OH eq. eq. CH2C12, 12h , rt -

2. HOONa 1.3

c

Re207 ,9

0

2,6-lutidine

OF

78%

OH

0

Boyce, R.S.; Kennedy, R.M. Tetrahedron Left., 1994, 35, 5133

1. SO(Im)2 OH 2. PhO- Li+

OH

34% OH D, Tetrahedron Lett., 1994, 35, 6279

El Arabi Aouad, M.; El Meslouti, A.; Uzan, R.; mere. OH

OH PhthNSCl , CHC13 , 60°C, 4d

SNPhth

64%

Me0

precursor to o-thioquinones Capozzi, G.; Menichetti. S,: Nativi. C,; Simonti, M.C. Tetrahedron Lett., 1994, 35, 9451

v H

Marson.;

HgO , dil. H2SO4 , 20°C Wll

0

Wll

-*

OH 73% Harper, S.; Wrigglesworth, R. J. Chem. Sot. Chem. Commun., 1994, 1879

1. t-BuLi , THF , -78OC 2. cyclohexanone ~T,.A,;

-

*

S

HO Dullweber, U.; Branan, B.M. Heterocycles, 1994, 37, 187

75%

264


1. Bu$nCH(OEt)z, BuLi THF , -78OC

PhCHO

Section 328

Ph

CH(OEt)z

c

I

2. aq. NH4Cl

OH 65% Parrain, J.-L.; Beaudet,I.; Cintrat, J.-C.; Duch$ne, A.; Quintard. J.-P,Bull. Sot. Chim. FL, 1994, 131, 304

(CFcO2)Re03 , O°C 2,6-lutidine , CH2C12

McDonald. FL; Towne, T.B. J. Org. Chem., 1995, 60, 5750

-OH

PhSeCl , CHCl3 -

LO,

= = XePh

W Cooper, M.A.; Ward. A.D, Tetrahedron Let?., 1995, 36, 2327

+

L,, ..

= = bH 36) quant.

OH OH

88%

2.H20

Corey. EL; Palani, A. Tetrahedron Let?., 1995, 36, 3485

S

J&l.

S,; Cho, C.M. Tetrahedron Let?., 1995, 36, 4845

HO

Section 329

(3-I

1

265

Alcohol - Halide

0

1.2% Cp2Ti(O4ClC&& , toluene 1% TBAF , Al2O3,5 PMHS , rt

w-h

0

OH

2.1M NaOH , TI-IF

* u PMHS = polymethylhydrosiloxane 94% (70:1) SLJ. Am. Chem. Sot., 1995, 117, 12641 Verdagauer,X.; Berk, S.C.; md. 0

BF3GEt2, NaBH3CN 6h .

0IOH 87%

.

Stlkrrshna. &, Viswajanani, R. Tetrahedron, 1995, SI, 3339 OMe

e’ , MeOH, aq. MeCN , Bu&IClO4 lh

OH 96%

Safavi. A.: Iranpoor. NJ Fotuhi, L. Bull. Chem. Sot. Jpn., 1995, 68, 259 1 REVIEW:

“Metal-Catalyzed Direct Hydroxy-Epoxidation of Olefins,” Adam. W,; Richter, M.J. Accts. Chem. Res., 1994, 27, 57


THIOL - HALIDE, SULFONATE

1. LDA. ZnCl2 , THF . -78OC mcl

2. PhCHO

80%

Cl Mallaiah, IS.; Satyanarayana,J.; Ila H,; Junjappa,H. Tetrahedron L&t., 1993, 34, 3145

a; 58,486

.

. 77) 74% (23 Furutani, H.; Ansari, M.H.; Sakai, T.; Utaka, M.; Takeda, A. J. Org. Chem., 1993,

266


Section 329

1. DibaI , CHg12, -78OC CF$@Et

83%

2.ZnBr2, BussF CHzCl2, 40°C T,; Hayashi, H.; Yamanaka, H. Tetrahedron Lett., 1993, 34, 5777

. ma.

MgBr2, Bu$IBH4 -

ether/CHglz:

72%

‘-Ph +

.Ph 22% “\Ph Bailey, P.L.; Briggs, A.D.; Jackson,R.F.W.; Pietruszka,J. Tetrahedron Mt., 1993, 34, 6611 Mg(NO& , Bu4NBr ,5h CHC13

OH

Y.-Q, Koo, B.-A.; Ko, J.-A.; Cho, Y.-S. Chem. Lett., 1993, 1907

93%

NaI04, NaHS03

k

Masuda, H.; Takase,K.; Nishio, M.; Hasegawa,A.; Nishiyama, Y.; Ishii. Y, J. Org. Chem., 1994, 59, 5550 Lick , DMF , 70°C , Id

Ph

-,jPhJ/H (35

+Lc1 ..

65)

Nymann, K.; Svendsen,J.S. Acta Chem. Stand. B., 1994, 48, I83 Br

PhCHO

OH CN

9 In

CN

84% (56:44 erythro:threo)

Araki, S.; Yamada, M.; Butsugan. Y, BUZZ.Chem. Sot. Jpn., 1994, 67, 1126

90%

Section 330

Alcohol - Ketone

267

REVIEW:

“Regioselectiveanbd ChemoselectiveSynthesisof Halohydrins by Cleavageof Oxiranes with Metal Halides,” m. C,; Righi, G. Synthesis, 1994, 225 SECTION

330: ALCOHOL,

THIOL

- KETONE

Rawal. VH,; Krishnamurthy, V.; Fabre,A. Tetrahedron Lett., 1993, 34, 2899 M F3

3

P 0

,,

15 min 96% Curci, R.; D’Accolti, L.; Detomaso,A.; Fusco, C.; Takeuchi. K.; Ohga, Y.; Eaton.& Tetrahedron Lett., 1993, 34,4559 TIPS

P

PhCHO , Me& rps

w

p”

88%

WPh Shoda,H.; Nakamura,T.; Tanino, K.; Kuwajima, I Tetrahedron Lett., 1993, 34, 6281

1. Me$i(OTf)Z , NEt3 m &

I

2. PhCHO ; Nishio, K. .I. Org. Chem., 1993, 58, 2647

HO*

78%

(919

syn:anti)

Ph OAc

OAc RuC13,MeCO# MeCN - Hz0 - CH2C12

78%

Murahashl. S.-I,; Saito, T.; Hanaoka,H.; Murakami, Y.; Naota, T.; Kumobayashi, H.; Akutagawa, S. J. Org. Chem., 1993, 58, 2929


xc

Section 330

H

0 0

’ acetone >96%

o”c

OH

OH (>98% ee , R)

D’Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci. R, J. Org. C&m., 1993, 58, 3600

0 II

1. BuLi , CO, -1lOOC THF/pentane/ether 2. rt , H30+ Hui, R.C.; Wang, W.-L. J. Org. Chem., 1993, 58, 5843

Sevferth.;

H PhCHO ,5% Sc(OTf)3, aq. THF *

Ph Y 83%

,; Hachiya, I.; Ishitani, H.; Araki, M. Synlett, 1993,472

Ph

PhCHO 2%

0

9 CH2C12

*

W&)3

PhU

Ph 84%

Ishihara, K.; Hananki, N.; Yamamoto. HJynlett,

1993, 577

0 PhwcHo

+

HMPA,rt,THF

, SmI

2 *

Ph*

0 83% (83:17 antixyn)

Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 959 -

MeC03H , cat. OsC13

Phv0I-I

Phv

MeCN-H20-CH2Q . Murahashl. S.-L; Naota, T.; Hanaoka, H. Chem. Lett., 1993, 1767

0

62%

269

Alcohol - Ketone

Section 330

PhCHO , A1203 ultrasound, 22h

..

(77 Ranu, Ike,

23) 75%

Chakraborty, R. Tetrahedron, 1993,49, 5333

PhCH2CH0 CHO

)

Phk

+

Ph;

H20, SmI2 OH

?)H

.

(39

61) 64%

Miyoshi, N.; Takeuchi, S.; Ohgo, Y. Chem. Lett., 1993, 2129

1.

==c

PhCHO

Bu

, EtCN , -78OC

20% chid acyloxyborane 2. aq. HCl

*

0

= =

Bu

Pha

81% (85% ee, R) Ishihara, K.; Maruyama, T.; Mouri, M.; Gao, Q.; Furuta, K.; Yamamoto. H, Bull. Chem. SOC. Jpn., 1993, 66, 3483

c

1

1. 2.2 eq. SmI3 , tetrahydropyran 2. propanal 3. H30+

0

-

H

c

0

95%

955

(trans:cis)

J.-L; Colomb, M.; Kagan, H.& Tetrahedron L&t., 1994, 35, 1723

OH

TFA , CDC13 ) 2d

ph 0

Dmhoux.;

Doris.


270


a Ph

Section 330

Cl

86%

3 eq. pyridine

C02Me

Araneo, S.; Clerici, A.; Porta. 0, Tetrahedron Lett., 1994, 35, 2213

P hl

OH

p)-(=)-oH

Cl

cat. HZSM-5 DCE , reflux

67%

HZSM-5 = acidic zeolite [SiO$A1203 = 401 Paul, V.; Sudalai, A.; Daniel, T.; Srinivasan.V, Tetrahedron Lett., 1994, 35, 2601 0

1. LDA , THF , -78OC 2. (iPrO)$Cl 3. acetone ,

>

8

II Ph 7

, -78OC

OH 5 1% conversion (88% yield)

4. aq. NH8

a.

W,; Mtiller, M.; Prechtl, F. J. Org. Chem., 1994, 59, 2358 OH

0

PhCHO , 10% Sm(hmds)J -30°C) 18h

Sasai, H.; Arai, S.; Shibasaki. M, J. Org. Chem., 1994,

UI -“iMe

VS.;

.

PhCHO , Yb(OTf)3

OH

aq. THF, rt , 19h

Hachiya, I. J. Org. Chem., 1994, 59, 3590

Ph 9 1% (73:27 syn:anti)

271

Alcohol - Ketone

Section 330

1. Me3A1, PhSeH 2. Me$=CHCH2CHO

92%x62%

w

3. BusnH, hv

I.-Y.C,; Lee, J.H.; Lee, H.W. Tetrahedron Lett., 1994, 35, 4173 OH

0

l.NaHMDS,THF * 2. PhCHO

Ph

Ph

+

.

(94

6)

69%

Goh, J.B.; Lagu, B.R.; Wurster, J.; J,iom. DC, Tetrahedron Lett:, 1994, 35, 6029 H 0

1, LHMDS , toluene-hexane t-Bu

2. Y(OTfl3,

HIIIIII -

OOC, 18h

t-Bu

x,

99% 0 crou. P,; Di Bussolo, V.; Favero, L.; Macchia, F.; Pineschi, M. Tetrahedron Lett., 1994, 35, 6537 i FfKfR-BINAPI

Ph-

, PhC12SiSiMe3,PhH Ph* w

0

l

3+

4. HBF4 5. H202 Matsumoto, Y.; Hayashi. T,: Ito, Y. Tetrahedron, 1994, SO, 335

OH

0

73~78%

, Yb(OTf-)3, 0°C 0

PhCHO

Ph

iPrmt , ether, 3h

92% (34:66 threo:erythro)

Fukuzawa. S.-i,; Tsuchimoto, T.; Kanai, T.. Bull. Chem. Sot. Jpn., 1994, 67, 2227


272

Jr

Ph

Section 330

OTMS OzMe -=c Me

BuflClOd , e’

SnBu3

*

Ph=

Yoshida. L; Morita, Y.; Ishichi, Y.; Ime. S, Tetrahedron Lett., 1994, 35, 5247

dPh

Enbolm.;

Sm1z2Br

94%

f”fPh

Schreier, J.A. J. Org. Chem., 1995, 60, 1110 PhCHO , MS 4A, 13h 5% PdClz[R-DINAPI-AgOTf *

23°C

Phu;

+

Phufi

87%

9%

Sodeoka,M.; Ohrai, IS.; Shibasaki. m J. Org. Chem.,1995, 60, 2648

‘: 0

, acetone, IX, ld 92%

OH 0 Bovicelli. Pa;Lupattelli, P.; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1995, 36, 3031

OHC Zn(NO3)2, acetoneHo Me2NCH2CH20H 30°C ,6h

pH 10.1 pH 11.0

98% 0%

Buonom. ET,; Rosauer,KG.; Dai, L. Tetrahedron Lett., 1995, 36,4o$I

0% 100%

Section 330

Alcohol - Ketone

273

H

K

1. Bu$nH , AIBN, PhH relux

0 -

Ph

2. PhCHO, 10°C, 12h

I

ti

73% (61 erytrho:threo) Enholm. EJ,; WhitIey, P.E. Tetrahedron Lett., 1995, 36, 9157

0

1. SmI2 Br

,

M%5 4

0

2. Hz0

OH

Ph Y

*

77% O Arime, T.; Takahashi, H.; Kobayashi, S.; Yamaguchi, S.; Mot-i. N, Synth. Commun., 1995, 25, 389 DMSO , KSF , microwave, 3 min Ph /\ . . lllemrn

0

OH 0

55%

DJ Hammadi, M. Synth. Commun., 1995, 25, 3141 0

Sm.

Ph *

1. LDA 2. Ti(OiPr)$l

53%

3. TBHP, BaO 4. NH8 , Hfl m; Kluge, R.; SchiiBer, M.; Hoffmann, G. Tetrahedron, 1995, 51, 3175 OH

$ A (CH2)7

Cl3CCO2H , 11°C , Cl2 , MeOH wh9

EtOH, NaHC03

0 w

r

98%

k (CH2)7

CgHW

Tassirznon. P.S.&; De Wit, D.; De Rijk, T.C.; De Buyck, L.F. Tetrahedron, 1995, 51, 11863

Br-COzEt

1.2 q. SmI2, -6OOC --+ -5O.C * 2. cyclohexanone , -50°C -+ 0°C

cC02Et OH

Utimoto. &; Matsui, T.; Takai, T.; Matsubara, S. Chem. Lett., 1995, 197

98%

274

Section 33 1


1. AlMe I Ph Aoki, Y.; ‘cr

Ph 79% (13:87 erythro:threo)

2. PhCHO i

I(.: Uti moto. K, Chem. L&t., 1995,463

Ph

PhCHO

-78OC ,6.5h Ishihara, K.; Hanaki, N.; Funawashi, M.; Miyata,M.; Yamamoto. 1995, 68, 1721


THIOL

Ph Bull. Chem. Sot. Jpn.,

- NITRILE

3: 1 EtCN-CH2C12, 1Oh 20% Mg-dihydrooxazolidine

c&3-cHo Corev.EJ.; ww,

OMS catalyst E * ca13>cN 12% bis-dihydro oxazolidine derivative z. Tetrahedron Lett., 1993, 34, 4001 H

4

CN

92h9* 100 units enzyme O.lM citrate buffer

NCHO

)

acN

93%Jz;Fon

enzyme = hydroxynitrile lyase from Hevea brasiliensis Klempier, N.; Ga; Hayn, M. Tetrahedron Lett., 1993, 34, 4769

80% Ohno, H.; Mori, A.; m. 02

88% (95%=, 9

S, Chem. Lett., 1993, 975 1. LiCH2CN 2. H30+ *

cl@21LCN73%

;fIaye. TJL; Crawford, K.B. J. Org. Chem., 1994, 59, 520

Section 33 1

Alcohol - Nitrile

0

275

1. TMSCN , CH2C12 , rt KCN/18-crown-6

0

2. MeOH/THF , SmI2

-

H”-(=)-cN 80%

Olson, S.H.; Danishefskv. SL Tetrahedron Lett., 1994, 35, 7901 OH 5

1. LDA , THF , -78OC

OH CN

ph-CN 2. PhCHO

*

Ph T

CN +

Ph hc

Ph Ph . 1) 70% (5 5 Carlier. P.R; Lo, KM.; Lo, M.M.-C.; Williams, I.D: J. Org. C’hem.,‘1995, 60, 7511 OH [ LDA , PhCH2CN ] , TMSCl

CN

PhCHO

97%

Zhou, J.J.P.; Zhong, B.; mennan.

Ph Rh J. Org. Chem., 1995, 60, 2261 HO

*

PhCHO Me$iCN

, Ti(OiPr)d 72% (91% ee, S)

Balm. C,; Miiller, P. Tetrahedron Lett., 1995, 36, 1625

GoI~~~-~H~ tm;

Cl Cl Zhmg, X.-L.; Han, Y .; Tao, W.-T.; Huann. Y .-2, J. Chem. Sot., Perkin Trans. l., 199% 189 Review:

“Catalytic Asymmetric Cyanohydrin Synthesis,” North. M, Synlett, 1993, 807

276

Section 332



THIOL - ALKENE

Allylic and benzylic hydroxylation (C=C-C-H -+ C=C-C-OH, etc.) is listed in Section 41 (Alcohols from Hydrides).

2 MeMgBr , CuCN BF3QEt2, THF

Bn

Bn -78OC

OH E z=

Me

=

88%

S-L; Lee, D-H.; Sim, H-S.; Lim, J-S. Tetrahedron Lett., 1993, 34,91 1. TIPSCl 2. MeLi -L PhCHO

0

.

JNEt2 yJ+L--yw

yj&

L 81%

Tsukazaki, M.; Snieckus. V, Tetrahedron Lett., 1993, 34,411 Lee, J.; Tsukazaki, M.; Snieckus, V, Tetrahedron Left., 1993, 34, 415 2SmI2,r-t 2 t-BuOH , THF

Me0

Me0

Me0

5 +

CHO 7r

I

(2 OH

.

..

3

OH

1) 66%

Glllmann. T, Tetrahedron Lett., 1993, 34, 607

SPh

BuLi , THF , -78OC t

C5Hll

OH Takano. S,; Sugihara, Y.; Ogasawara, K. Tetrahedron Lett., 1993, 34 845

5% DTBB , THF, O°C

i

I

only product (90%)

OH

D.&; Kim, K.; Martinez, J.P. Tetrahedron Lett., 1993, 34, 3071 1. PhCHO , DMF , 0°C wSC13

y

-

., OH = = Q = = = t.

2

97)

Kobavashi. S,; Nishio, K. Tetrahedron L&t., 1993, 34, 3453

10 eq. BuLi , 10 min )

89%

71%

OH

Bu

Lautens. M,; Gajda, C. Tetrahedron Lett., 1993, 34, 4591 BI-j

B

/-Br

rJ

C&CHO

, EG-Zn e

DMF , O°C ,2h

C3H3

72% EG-Zn = electrogenerated reactive zinc Tokuda. M,; Mimura, N.; Karasawa, T.; Fujita, H.; winome. 7607

H, Tetrahedron L&t., 1993, 34,

PhCHO , hv (>320 nm) EtCN , -78°C ,5h E-snBu3

-

A+&

+ EthPh (30

muwa.

..

k; Shiigi, J.; Nishigaichi, Y. Tetrahedron Mt., 1993, 34, 3457

70) (86: 14 E.z)

278


Section 332

Et2Zn , Ti(OiPr)d , 12h -6OOC + -55OC

d \

8%

,Ti(OiPrb

(93% ee)

Y

Rozema, M.J.; Eisenberg, C.; Liitjens, H.; Ostwald, R.; Belyk, K.; wel. LAt., 1993, 34, 3115

4

P, Tetrahedron

1,2dichlorobenzene , 12h reflux , CO.5torr

llllI~lll

t

Q

=

90%

bH

*

\

OH Janardhanam, S.; Devan, B.; RaiogoDalan. K, Tetrahedron L&t., 1993, 34,676l 1. Sharpless epoxidation 2. TsCl

Ph OH

78% (>90% ee)

3. Te , LiBHEt3 , THF TBAF,lt

* \ - D-c; Discordia, R.P.; Zhang, Y.; Murphy, C.K.; Kumar, A.; Pepito, A.S.; Wang, Y. J. Org. Chem., 1993, 58, 718 Bu

iPrMgBr , THF Bu

wJP)2Ni2c12

Ducoux, J.-P.; LeMenez, P.; tine&

Bu *

+

h

(CH2)2CH20H

w

u-mCH20H (>25 1) 60 N... Wenkert. E, J. Org: Chem., 1993, 58, 1290

MeJSiSnBu3 , DMF 86%

CsF, rt, lh *b mu;

OH Isono, N.; Kaneta, N.; Shibasaki, M. J. Org. Chem., 1993, 58, 2972

Section 332

Alcohol - Alkene

279

OH w

hv,CO,THF,8h

c. CA;

75

Xu, D.; Gladstone, B.G. J. Org. Chem., 1993, 58, 538

0

EtMgBr , 10% Zr complex THF ,25*C

0

Morken, J.P.; Didiuk, M.T.; Hove-

OTMS

65% (>97% ee) A.H, J. Am. Chem. Sot., 1993, 115, 6997

5% (binol)TiClz , BnOg-CHO C02Bn Me

63% (99:l syn:anti; 99:l ZE; 99% ee, R) Mikami. K.; Matsukawa, S. J. Am. Chem. Sot., 1993, 115, 7039

‘* --cbv

SiMe3 ’ “:‘igchiral ligmd

phu

*

PhCHO

Z = = 63% (92% ee)(96:4 erythro:threo) bH Ishihara, K.; Mouri, M.; Gao, Q.; Maruyama, T.; Furuta, K.; Yamamoto, H,J. Am. Chem. sot., 1993, 115, 11490 2. TBAF

OH --i=h’

, 10% Pd(OAc)z

2 Na02CH ,2 BuflCl ,2 iPr2NEt MezNCOMe ,8O*C, Id ~R.c.;

Ding, S.; Tu, C. Synlett, 1993, 145

70% (5644 E.-z)

280


Section 332

x= Sin&ton.

D.A,; Redman, A.M. Tetrahedron Lett., 1994, 35, 509

&,gmak. J.D,; Geng, B.; Uang, S.; Strickland, J.B. Tetrahedron Lett., 1994, 35, 985 1. Cp$Zr(H)Cl , CH$12 2. Me2Zn

Bum

3. PhCHO , O°C

Bu 94%

WiDf. P,; Xu, W. Tetrahedron Lett., 1994, 35, 5197 /\/\oO

2eq. Me#=CH2

,THF

*

z

-1OOC + rt 80% OH Alcaraz, L.; Hamett, J.J.; Mioskowski, C.; Martel, J.P.; Le Gall, T.; Shin, D.-S.; Falck, J.R. Tetrahedron Lett., 1994, 35, 5449

0 /

/

1. ($-C$-I,hTiCl \

iPrMgC.1, THF , -50°C 2. PhCHO , -50°C +

= -20°C

@Ph+

@Ph (1.44

:

1) 42%

Szymoniak, J.; Felix, D.; Moi’se. C, Tetrahedron Lett., 1994, 35, 8613

1. HSiC13 , cat. Pd(PPh& 2* Phw

CHo , DMF

Kobavashl, . S .; Nishio, K. Synthesis, 1994, 457

Ph 87% (>99: 1 syn:anti)

Section 332

Alcohol - AIkene

phCN,Nyluene9

281

refhx, 3hwfiMe 73% Ph

(3:2 synxnti)

Kim. S,; Cho, C.M. Tetrahedron Lett., 1994, 35, 8405

Pd(OAc)z ,3 PPh3 , PhH 7O*C, 16h

CHO

-5

OH 47% Watanabe, T.; Sakai, M.; Miyaura, N.; Suzuki, A,.!. Chem. Sot. Chem. Commun., 1994,467 OH

BuMgBr N-NHTs

* .,,t5L Takhi, M.; Yadav, J.S. Tetrahedron Lett., 1995, 36, 307

Chandrasekhar.,

1. Li , NH3 , THF-EtOH 2. TBAF , THF

Bu

, -78OC

\* ,, ,*’ *

3.30% aq. H202, KHCO3 , MeOH OH Taber. D.F*; Yet, L.; Bhamidipati, R.S. Tetrahedron Lett., 1995, 36, 351

5% Pdz(dba)3*CHC13 , THF 20% PPh3 , heat \ MpM(,o

OH

93% KanG S-K,; Park, D.-C.; Park, C.-H.; Hong, R.-K. Tetrahedron Lett., 1995, 36, 405 Phs

1. Cp2TiClz/2 BuLi , 0°C 2-

ma.

PW

CHO

T,; Miura, I.; Horikawa, Y.; Fujiwara, T. Tetrahedron Lett., 1995, 36, 1495

282


Section 332

Co(tdcpp) = [5,10,15,20-tetrakis(2,6-dichlorophenyl) porphinato] Cobalt (II) -Y.; Sugamoto, K.; Nakama, T.; Sakamoto, T.; Matsui, T.; Nakayama, M. Tetrahedron Lett., 1995, 36, 18’79 Ph

Ph 3 t-BuOK, BuLi THF , -78OC

OH *

R=TBS (79 R=H (20 Tomooka, K.; Keong, P.-H.; Nakai. T, Tetrahedron L&t., 1995, 36,

.. .

21) 48% 80) 90%

&89

1. BuLi, THF , -78°C 2. PhCHO, -78OC -+ rt

+

PhxH

/= 85%

MO, X.-S.; uuang. Y.-Z, Tetrahedron Lett., 1995, 36, 3589

&

OMe Dibal , 14% Ni(cod)z 20% R-BINAP , lh i-l

OMe

*

H

htens.

78% (97% ee) M; Chiu, P.; Ma, S.; Rovis, T. J. Am. Chem. SOC.,1995, 117, 532

‘OMe

Aldehyde - Amide

Section 335

283

Ph SnCb-NBu3 , MeCN reflux Yamaguchr. b&; Hayashi, A.; Hirama, M. J. Am. Chem. Sot., 1995, 117, 1151

S.-K,; Park, D.-C.;

Rho,

H.-S.; Yu, C.-M.; How

J.-H,Synth. Commun., 1995, 25,

203 OMe =c

PhCHO .

9 10%Ti(OiPr)d

20% chiral binaphthylamine

Bemsford.

.

C, Angew. Chem. Znt. Ed. Engl., 1995, 34, 1717

Also via:

Section 302 (Alkyne - Alcohol).

SECTION 333: ALDEHYDE

- ALDEHYDE



- AMIDE

S02Ph

SO2Ph Brown, S.; Clarkson, S.; Grigg. RJ Sridharan, V. J. Chem. Sot. Chem. Commun., 1995, 1135


- AMINE Cl DMF , POC13 8%

Balasundaram, B.; Venugopal, M.; Permumal.P.T, Tetrahedron Lett., 1993, 34,4249

284



- ESTER

NO ADDITIONAL


EXAMPLES

- ETHER, EPOXIDE, THIOETHER

ct

Wp-OMe)2KOD)2

10 eq. PPh3 , CO, H2

+

+ HC(OEt)3 ,2d (96 + HC(OEt)3 + PPTS ,12h (0 Femandez, E.; B. S, Tetrahedron Lett., 1994, 35, 2361 2% Pd(PPh3)4,5 atm CO, THF C5Hll

4) loo)

PhSH , 70°C , 16h

Et0 quant. quant.

CHCHO PhS

Ogawa. &; Takeba, M.; Kawakami, J.; Ryu, I.; Kambe, N.; &poa 1995,

82% (13:87 E.-Z) N, J. Am. Chem. Sot.,

117, 7564


- HALIDE, SULFONATE

NO ADDITIONAL



EXAMPLES

- NITRILE

NO ADDITIONAL


EXAMPLES

- KETONE

NO ADDITIONAL

EXAMPLES

- ALKENE

For the oxidation of allylic alcohols to alkene aldehydes, also see Section 48 (Aldehydes from Alcohols).

CHO

1. Cp$r(Cl)CH=CHOEt cat. AgClO4

2.H3O+ oMaeta, H.; Suzuki. K, Tetrahedron Lett., 1993, 34, 341

OEt

C5h *

L

Section 341

285

Aldehyde- Alkene

Section 341

Li 1.

OMe

-78OC+ 0°C

PhCHO 2.1N

*

CHO P

HCl , OmC

75%

Duhamel, I,,; Duha.mel,P.; Le Gallic, Y. Tetrahedron Lett., 1993, 34, 319

OTMS 0 I

-

OTMSCAN, MeCN , O°C

Paolobelli, AX; Latini, D.; Ruzziconi.

25%

CHO


polymeric Fe catalyst

Saha,AK.; Hossain. M.M, Tetrahedron Lett., 1993, 34, 3833 Br

CHO 6\

/

9 (3-W& 79%

cyclic B catalyst, -78°C ,8h

(99:l exxendo) ,92% ee Corev. E.J,; Loh, T.-P. Tetrahedron Lett., 1993, 34, 3979

PhCHO

CsF-DMSO , rt + loO°C

*

PWCHO

ZnClz, rt ,2h &; Salemkour, M. Tetrahedron Lett., 1993, 34, 5281

70%

2.

md.

7=-i

PhCHO ,5% TfSiMe3 CH2C12, rt ,15h

P

v MqSi CHO OSiMe3 Duhamel. L; Gralek, J.; Bouyanzer, A. Tetrahedron Lett., 1993, 3% 7745

80%

Com~n~um of Organic Synthetic Means, Vol9

286

N-t-Bu md.

WI,: 1187

PhCHO , 10% ZnBrz , THF

(Me3Si)zHC J a; Majidi, A. J, Org. Chem., 1993, 58, 2517 m

/CHO

Section 341

SnBq

, CgHlyBr, AIBN

20 atm. CO, PhH , 80°C, 8h

Yamazaki, H.; Ogawa, A.; Kambe, N.; ma.

1.

9 0

74% N, J, Am. Chem. Sot., 1993, 115,

, acetone

a2. PH3P=CHCH0, CH2C12

‘“~0, 84%

Adger, B.J.; Barrett, C.; Brennan, J.; McGuigan, P.; Wervey. Commun., 1993, 1220

M.A, J. Chem. Sot. Chem.

HO , SmI2,25OC

CHO (955 Van de Weghe, P.; collin,

[1,4:1,3])

72%


Bu 1. Bu$H , TiCI , CH2Cl2 2. F’OC13 , DMF , O-5OC

67%

*

~

CHO

Asokan. CV,; Mathews, A. Tetrahedron Lett., 1994, 35, 2585

75 Derien, S.; Dixneuf. P.I-I, J. Chem. Sot. Chem. Coals.,

25) 85%

: 1994, 2551

Ph-OH

287

Amide - Amide

Section 342

Pd(PPh3)4 , NH4PF6 , toluene - phmcHo 02 , heat

90% Gomez-Bengoa, E.; Noheda, P.; Echavarren, A.M. Tetrahedron Lett., 1994, 35,7097 Et0

SnBu,

1,

PhCHO

ph/n/CHO

BF3mOEt2, CH2C12, -78OC, lh 86% Cabezas, J.A.; Oehlschlaner. AC, Tetrahedron Lett., 1995, 36, 5127

.

Mn02, hexane, 15 mm

ph-N,OH

*

phmCHo 87%

Shinada, T.; Yowa.

L Tetrahedron Lett., 1995, 36, 6701 CHO Ru (indene)Cl(PPhg)z

88%

-i_i

Ph

Ph

Trost, B.M.; Livingston, R.C. J. Am. Chem. Sot., 1995, 117, 9586 CHO

2% [ Rh(CO)z(acac) ] +

C3H-W7

2.2% biaryloxyl phophite

Johnson, J.R.; Cuny, G.D.; mwald.

SLAngew.

A C3H7

w7

85% Chem. Int. Ed. Engl., 1995, 34, 1760

Also via P-Hydroxy aldehydes: Section 324 (Alcohols - Aldehyde).

SECTION 342: AMIDE - AMIDE NO ADDITIONAL

Also via Dicarboxylic Acids: Diamines

EXAMPLES

Section 312 (Carboxylic Acid - Carboxylic Acid) Section 350 (Amines - Amines)

288


Section 343

SECTION 343: AMIDE - AMINE Me C=N

AcCl , Ac20 , HCl 63%

100-130°C) 4h

NHAc Me Vijn. R.J,; Arts, H.J.; M aas, P.J.; Castelijns, A.M. J. Org. Chem., 1993, 58, 887 l.TMSCI,NaI,12 TMEDA , MeCN 2. NH3, loO°C 3. racemization-resolu tion

o-II& K.L; Keller, J.L.; Purick, R.M Hartner Jr., F.W.; Choi, W.-B.; Askin, D.; Volantei R.P. Tetrahedron Mt., 1994, 35, 32i9 l

TsHN \

Pd(OAc)z , EtzNH latmCO,THF

P

,-Ts

CH2Ch

. Andersson. PeGI; Aranyos, A. Tetrahedron Lxtt., 1994, 35,444;

/ \ I q

14) 72%

Me -7OOC + -2OOC

N

I N

t Ph

OZnCl OMe

Me0

58%

Me van Maanen, H.L.; Kleijn, H.; Jastrezebski, T.B.H.; van Koten. G, Reel. Trav. Chim. Pays-Bas, 1994, 113, 567

Section 344

Amide - Ester

T

289

S

N

BnNH2,10%

NHTs

Yb(OT&

CH2C12, rt, 1Oh

NHBn

ANHBn

‘arts

A

(>99 : 1) Meguro, M.; Asao, N.; Yamamoto, Y. Tetrahedron L&t., 1994, 35, 7395

CL N

0

t-BUN& , NEt3

)

0%

N

75%

0

78%

CH2C12, reflux , Id I Cl NHt-Bu Chen, P.; Suh, D.-J.; Smith. M.B, J. Chem. Sm., Perkin Trans. I., 1995, 1317 L

SECTION 344: AMIDE - ESTER t-BuBr , KgO3, DMAC BTEAC ,55OC * Boc

92%

BocH DMAC = dimethyl acetamide BTEAC = BuEt3NCl Chevallet, P.; Garroust, P.; Malawska, B.; Martinez. J. Tetrahedron L&t., 1993, 34, 7409

Mn(OAc)3 , CH$O2Me)2

Chuang. C-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 1283

a;

Lee, S.J. Tetrahedron Lett., 1994, 35, 1875

290

Section 345

Compendiumof Organic Synthetic Methods, VoI9

1.15% ZnCl2 CH2C12 2. CAN, M&N, CO

Ph

Ph Chen, T.; Jiang, S.; mos. E, Tetrahedron Lett., 1994, 35, 8325

Y

Cl

CO2Me Bu3SnH , AIBN , PhH *‘h0

N’Bn

Ph “i( 0

N I Bn

2:

C&Me

Ph 0

52% Goodall, IL; Parsons.A.F, J. Chem. Sot., Perkin Trans. I., 1994, 3257 0

1. Sn(OTf)z CHz,Clz

0

C02Me

~

N-- Et

c

2.

N

**

c-l

I

OEt

COzMe

C02Et

‘;J

CO,Et

78% Nagasaki; Nishida, S.; Sugihara,S.; Kawahara,T.; Adachi, K.; Hamaguchi,F. ~etero~c~s, 1994, 39, 171 Section315 (Carboxylic Acid - Amide) Section316 (C~~xy~ic Acid - line) Section 351 (Amine - Ester)

RelatedMethods:

SECTION

345: AMIDE

- ETHER,

EPOXIDE,

THIOETHER OH

CO/H2 (1600 psi) ,loO*C HC(OEt)3,24h H~(CO)(PPh)3 OSiMe3

42% OEt

0

(2: 1 syn:anti)

Eguchi, M.; Zeng, Q.; Korda, A.; Qiioma. I, Tetrahedron Lett., 1993, 34, 915

291

Amide - Ether

Section 345

1.

P-O H

Ph Ph

J3H3,TNF

w

2. H+ , EtOH Bn Romagnoli, R.; Roos, E.C.; Hiemstra. H,; Mollenaar, M.H.; Sneckamp,W.N.; Kaptein, B.; Schafer, H.E. Tetrahedron Lett., 1994, 35, 1087

H

Ar

Ar = 4-nitrophenyl; Ar’ = 4-t-butylphenyl

95% (66% ee) Hayashi, M.; Ono, K.; Hoshimi, H.; Qgni. N, J. Chem. Sot. Chem, Commun., 1994, 2699

cyclohexanone, H$X&

CN AcOH , Ac20, 10°C , Ih a&. J.-F,; Jung, L.; Hug, R. Heterocycles, 1994, 38, 297

cat. ZnC12, CH2C12,50°C16d ~y~e~ic

Pummerer rearrangement

; Shibata,N.; Kawano, N.; Tohjo, T.; Fujimori, C.; Matsumoto, K. Tetrahedron Lett., 1995, 36, 115

Section 346


292

C@Me

Amlres, C.J.; Spetseris,N.; Norton

SECTION 346: AMIDE - HALIDE, SULFONATE

Cl * l-L?Cl

Cl

CuCl , cat. bipy

98%

0

N

I Bn

Nagashima,H.; Ozaki, N.; Ishii, M.; Seki, K.; Washiyama,M.; Itoh, K. J. Org. Chem., 1993, 58,464

Et3N*3 HF , MeCN

77%

t e”

Narizulca, S.; Fuchierami. T, J. Org. Chem., 1993, 58, 4200

IP

Ph#e(OH)OAc , I2 hv ,6Sh ;)

0

I

I

76% Dorta, R.L.; Francisco, C.G.; Suarez. IE,~etr~he~~~~ Lett., 1994, 35, 1083

a

NPh2

w ~

.

h/L; m

1. b-AnP(S)S]z, PhMe , lOO*C 2. Bum2F3, NIS , CH2C12 o”c -+ l-t T, ~etr~he~~u~ Lett., 1994, 35, 3983

F w w

x

F

NPh2 98x64%

Section 347

Amide - Ketone

293

C3H7

0 b Nt

0

-7VC, 6h BC120Me

ind Jt-

1) 80% o. G,; Di Martino, E.; Gentilucci, L.; Tomasini. C,; Tomioni, L. Tetrahedron Asymmetry, 1995, 6, 1957 (>99

l

SECTION 347: AMIDE - KETONE

0

2DMP,4Py,lh CH2Clz, rt

N

Dess-Martin

ti

)

0 N

0

periodinane

Ph

75%

Ph

,hyr DMP = 1,1,l-triacetoxy-l,l’-dihydro-l,2-benzodoxol-3(1H)-one Batchelor, M.J.; Gillespie, R.J.; Golw. J.M.C,; Hedgecock,C.J.R.


30% H202, Pd(OAc);! CH2C12,rt ,2h -

73% *

Naota, T.; Sasao,S.; Tanaka,K.; Yamamoto,H.; Murahashl.. 4843

0

0

ii Tetrahedron Lett., 1993, 34,

OEt

w

c

0 TFA , 20°C, Id N

NT -* 0 Br 0 J.-P*;Jacquesy,J.-C.; R~nbaud, D. Tetrahedrons 1993, 49, 2239

47%

Section 347


294

Bu$nH, AIBN, PhH (syringe pump addition) a 91%

Beckwith. A.L,J,; Joseph, S.P.; Mayadunne, R.T.A. J. Org. Chem., 1993, 58, 4198

1. 3 Mn(OAc)3 2. H30+

+

h /

N

cossy. J,; Bouzide, A.; Leblanc, C. Synleft, 1993, 202 OTMS Me$iOTf

NMeC02Mk

, NEt3

NMeC02Me

O°C , lh Rossi, L.; J?ecumo. OMe

A, Tetrahedron Lett., 1994, 35, 5285

)I

Hewawasm

3.12N HCl-DME , reflux /

Me 0

1. BuLi, THF, O°C 2. (C02Et)2

\ I b

85%

\ I fi

0 /

NHCOzt-Bu P,; Meanwell, N.A. Tetrahedron Lett., 1994, 35, 7303

PhCH=NC02Et,

BF3eOEt2

CH2C12, rt ,2d ten Hoeve, W.; Wynberg, H. Synth. Commun., 1994, 24, 899

N \ H

80x88%

section 347

Amide - Ketone

295

Me I

1. Me~OH

Ph

0 N-Me

2.

60% via heteroCope 3, Hz0 Lantos, I.; Zhang, W.-Y. Te~$~~e~r~~ L&t., 1994, 35, 5977 0

OMe Si(iPr) 3

1. RCOCl 2. MeMgX 3. oxalic acid 4. TFA , CHC13, heat + ,yyi+* ,\* i) N

I

I 78~86% I CO2R

R = (-)m8-phenylmen~yl Comins. D.L,; LaMunyon, D.H. Tetrahedron Lett., 1994, 35, 7343

1. t-BuLi , TMEDA , -78OC NiPr2

t 2.

Brenstrum, T.J.; Brimble. M.A,; Stevenson,R.J. Tetrahedron, 1994, 50, 4897 0

NHAc

\ I /I phi 0

CoCl2, MeCN, AcCl

Bhatia, B.; Reddy, M.M.; Iqbal. J, J. Chem. Sot. Chem. Commun., 1994, 713 b

NfIMe

4 eq. DMAP , toluene , reflux

N

/

Me

w

c0ssv.z.; Belotti, D.; Bouzide, A.; Thelland, A. Bull. Sot. Chim. Fr., 1994, 131, 723

NO2

Section 349


2%

0

* 0”

l.e-,AcOH,heat 2. MeOH, NazCO3

0

75x95% N N I I C02Me C02Me Matsumura. Y.; Takeshima, Y.-i.; Okita, H. BUZZ.Chem. Sot. Jpn., 1994, 67, 304

iPrCH0, AcCl ,02, CoC12 = Reddy, M.M.;

MeCN Bhatia, B.; -1.

76%

J, Tetrahedron Lett., 1995, 36,4877

0 cat. [Rh2(OAc)4] B-‘&/2

=: = z

*

59%

Ge Podlech, J.; Seebach. D, Helv. Chim. Acta, 1995, 78, 1238

SECTION 348: AMIDE - NITRILE 0

0 CN

IIZN JL

Ph

CN

DMSO, O2 Ph

88% Jain, R.; Roschangar, F.; Ciufolini. M.A, Tetrahedron Lett., 1995, 36, 3307

SECTION 349: AMIDE - ALKENE

.. (6 Khiar. NJ Femandez, I.; Alcudia, F. Tetrahedron L&t., 1993, 34, 111

4

78%

297

Amide - Alkene

Section 349

1. LDA , THF , -78OC ApcPh

92%

PhR 2. PhCHO , THF Ph I /q II I ph reflux Me Me 0 ; Deniau, E.; Grandclaudon,P. ~~tr~h~~ron Lett., 1993, 34, 1479

0\ /

0

0

lm%z

, MS481, CH2C12

0

*

20% chiral Yb triflate , O°C

~~ .

I(lobavashl.;

(89: 1 en.do:exo; 95%ee) Hachiya, I.; Ishitani, H.; Araki, M. tetrahedron Lett., 1993, 34, 4535

4% Pdz(dba)3eCHC13 9.6% RS-BPPFOH silver~xch~ged zeofite c ~~ ~

D~:DMSO

0 (1

0

Tetrahedron ktt.,

Nukui, S.; Sodeoka,M.;

Bf R -dFoEt

+

, WC, 5d

\

*.

1.4) 94% (86%ee)

1993, 34,4965

, PPh3 /n-IF

Ph

f14$.?

R

Ph

2% Pdz(dba)3~HCl3 2 eq. iPr2NEt

OEt

-

g

0

N \

73%

Bn Torii. &; Okumo~, H.; Sacked M.; Hai, A.K.M.A.; Tanaka, H. tetrahedron Lett., 1993, 34, 6553

0\ I

) -20”C, 36h

Ph

w

b&imine*cu(OTE)2 (>97:3 en.do:exo) 72% Evans. D,A,; Lectka, T.; Miller, S.J. Tetrahedron Mt., 1993, 34, 7027

298

Section 349


1.. 0.2 eq.fe(acac)s 3 eq. EtjAI/L

0

o+

2. ethylene glycol cat. p-TsOH cc BzO

ws.

m;

Weidner, J.J.; Takacs, B.E. Tetrahedron Mt., 1993, 34, 6219

0.02 PdC12,2 eq. CuCL2 3 eq. ClCH,CQ-Na+ NHTs 9(

C02Me

CO. MeOH

N\

53%

Ts

Y

0

0 Kimura, M.; Saeki, N.; Uchida, S.; Harayama, H.; Tanaka, S.; Fugami, K.; Iama~~ Y, Tetrahedron Lett., 1993, 34, 7611 1. Et02C-N=N-COzEt , SnC4 CH2C12, -60°C, 5 min

2 N-J-N

*

*mC02Et

2. Li , NH3 , -33°C 3.10 N HCl Brimble, M.A.; -cock.

CL

87 x 86% (1l:l

E:Z)

J. Org. Chem., 1993, 58, 5261

Br Pd(OAc)z , P(o-ToI) , DMF Na$ZOs, BUflCl ,65”C, 40h sealed tube (in vacua) 4iEs+

&

1) (4 Harris Jr., G.D.; Herr, R.J.; Weinreb. S.M, J. Org. Chem., 1993, 58; 5452 l

78%

Amide - Alkene

Section 349

299

Pd(PPh3)4,PhMe ,lOO°C Trost. B.M; Marrs, C.M. J. Am. Chem. Sot., 1993, 115, 6636 COzBn Ph$‘=CHCO2Et *

80%

toluene , reflux ,4h

Et0 \ ~ Ba: 0 BOC Baldwin. JE,; Edwards, A.J.; Farthing, C.N.; Russell, A.T. Sy~lett, 1993, 49 CO2Me

1. NaH , THF , BuLi CO2Me Ts

>96% (>20:1 E=z)

3. toluene , Amberlyst 15 , reflux &p

B, Sy~~ett, 1993, 764 Ph PhCH2m2Et

Ph

1.2 eq. LDA 2. Ph~H=NPh

*

PhHN 7

58% 0 this reaction forms a p-lactamwith 1 eq. of LDA Manhas. M.S; Chaudhary, A.G.; Raju, VS.; Robbi, E.W.; Bose, AK. HeterocycZes, 1993, 35, 635

1. xylenes , reflux 2. PPTS NaH , DMF THPO’ De la Torre, J.A.; Femandez,M.; mJr.. Tetrahedron Lett., 1994, 35, 15

60% 68~75% D,; Smith, D.B.; Talamas,F.X.; Trejo, A.

OMe Zn,THF,rt,lh NHCaMe Kise. N,; Yamazaki, H,; Mabuchi, T.; Shono, T. Tetra~e~r~~ Lett., 1994, 35, 1561

300

Section 349


79% W,; Fiirstner, A. Helv. Chim. Actu, 1993, 76, 2329

Qpolzer.

1. piperidine , CF3C@Ag --YSPh

THF’rt 2. CgHl@gBr NiCl,(dppe)

6

* csH1& , THF , 0°C + rt 57x60%

a

B&u&-i, F.; Fiandanese.V,; Naso, F.; Punzi, A. Tetrahedron Lett., 1994, 3.5, 2067

6 i/

PhMe2CCH=Mo-N[2,6-(iPr)2C6H13] [ocMe(CF3)212

N-0

I

a@

PhH,rt

0

80-90%

/

n. S.F,; Liao, Y.; Chen, H.-J.; Patzel, M.; Ramser,M.N. Tetrahedron Lett., 1994, 35,

&‘Ph3

SO2Ph

Burley, I.; Hewson. A.T, Tetrahedron Lett., 1994, 35, 7099

COzt-Bu

C02t-B u 52% (9O:lO E:Z)

Wei, Z.Y.; m.

EL Synlett, 1994, 345

Section 349

Amide - Alkene

301

0 ==cIl N

, MS 4A, CHg12

alto

N CA

/ N

20% Yb-BINOL complex 7

0

c-J== 0

Me

0

.t

(89

11) 77%

95% ee Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett., 1994, 35, 6325

.

WS.;

0

C02Et NH2

1. C02Et

.

Me”“’ rl Ph

H

, BF3GEt2, PhH , reflux

2. CH2=CHC02C@,

0

TI-IF , reflux

+Jz+If2

N

Me”““’ri Ph

H 76% (97:3)

Barta, N.S.; Brode, A.; Stille. J.R,J. Am. Chem. Sot., 1994, 116, 6201 Ar NH2

H2C0, [Rh(OAc)d2, PPh3, PhH -Iso 0

N I 40% H Campi, E.M.; Chong, J.M.; Jackson. W.R,; Van Der Schoot, M. Tetrahedron, 2994, 50, 2533 Ar

aI/ \

NHTs

I

I

Ts CsI-I17--CH=C=CH2 Ag3P04, 5% Pd(OAc)z

/ w-h7

his-oxazoline catalyst 90°C, Id, DMF 94% (82% ee)

Larock. RC,; Zenner, J.M. .I. Org. Chem., 1995, 60, 482

302


Section 349

Ph-N=C=O , AlC13 ,4O”C Men&Me

ti

NHPh

Me 9

3

CH2C12, 12h 0 Niestroi. M,; Neumann, W.P.; Thies, 0. Chem. Ber., 1994, 127, 1131

50% (4.9:1 E:Z)

BQNF ,66OC

Bn Jacobi. P.A,; Brielmann, H.L.; Hauck, S.I. Tetrahedron L&t., 1995, 36, 1193 Bu 5% C12Pd(PPh&, MeOH, 65OC *

CO (1 atm) ,4 NEt3

AcAB’

ci,

0

N I AC

78%

Coperet, C.; Sugihara, T.; Nenishi. E, Tetrahedron L&t., 1995, 36, 1771 phwTePh

TsNNaCl , EtOH ,20h 25OC

Nishibayashi, Y .; Srivastava, SK.; Ohe, K.; Ueu

c),

-‘“‘f‘

+PhyNHTs

OH 9% 84% Tetrahedron Lett., 1995, 36, 6725

1. LiHMDS , THF , HMPA , -78OC 2. PhNTf2, -78OC + 25OC

cl

t

N o 3. PhguLi , THF-HMPA I -78OC + 25OC Bz Tsushima, K.; Hirade, T.; Hasegawa, H.; Murai. A, Chem. Lett., 1995, H Me+,,,,

I 9(

Me 0.1 AgNCO , 0.1 NEt3 , PhH 50°C, 5h NHTs

N I Bz 801

94x69% Ph

-w/r”“’ N-Ts

-lf

0 0 Kimura, M.; Tanaka, S.; Tamaru, Y kBull. Chem. Sot. Jpn., 1995, 68, 1689

98%

Section 350

Amine - Amine

303

Also via Alkenyl Acids: Section 322 (Carboxylic Acid -Alkene)

SECTION 350: AMINE - AMINE In , aq. EtOH , 16h ) NH&l

N /Ph PhJ

Ph Ph NHPh quant.

NHPh Kalvanam. N,; Rao, G.V. Tetrahedron Lett., 1993, 34, 1647

Plaquevent. J.-C,; Chichaoui, I. Tetrahedron Lett., 1993, 34, 5287 NH

PhCN H

quant.

* G+ Ph Rousselet, G.; Candevielle, P,; Maumy, M. Tetrahedron Lett., 1993, 34, 6395

NHEt2 ,0.8 GPa , CH2C12 ,2d MeOH, 50°C \

H

68% H Matsumoto. K,; Uchida, T.; Hashimoto, S.; Yonezawa, Y.; Iida, H.; Kakehi, A.; Otani, S. Heterocycles, 1993, 36, 2215

/

Br

1. t-BuLi , -78OC , THF 2.ZnC12 3. PdC12(PPh3h , Dibal THF , reflux * w

SiMeg-Bu

Br

/

\ Ior) \

4. TsOH , EtOH Amat, M.; Hadida, S.; Bosch., J. Tetrahedron Lett., 1994, 35, 793

/

93%

N \ SiMe$-Bu


304

AI,KOH,MeOH,rt,lOmin 2 ph-

Section 351

Ph

Ph

t

NPh

PhHN Baruah, B.; ~ajapa~, ID.; mu.

NHPh

90% (70:30 dlmeso) J& Tetrahedron Lett., 1995, 36,6747

(95 N&

Nh

. OH Ar = 4-OMe phenyl Shimizu, M.; Kami, M.; EU,jisawa.T, Tetrahedron Lett., 1995, 36, 8607

5) 71%

l

SECTION 351: AMINE - ESTER

C

1.

COzEt ~echoech~;

COzEt

I”

2, SmI2, THF ,25OC 70%

Fem~~dez-Acebes, A. Tetr~~dro~ Lett., f993,34,549 Ph \

N I

1. ImzCO , BF3*OEt2

PhHN

84%

c( 7

TMS

AgF , EtOAc >

s

MeCN , rt 15 min TM:

(17 m.

COzMe

‘t

THF , heat Y 2. NaOMe , MeOII/THF 94% ph S,; D&u, M.D.; CarkSn,R.P. Tetrahedron Lett., 1993, 34, 725 PhA

m.

N-H

(7:3 de) G; Lakshmaiah,G. Tetrahedron Lett., 1993,34,4861

..

SC ss, C02Et 3)

98%

Section 351

305

Amine - Ester

I\ P

1.

, BEt3, DMSO C02Et

54%

Fe2(SO)3~H20, hexane

. Me ch;L,E;,Muraglia, E. Te~rah~dru~ Let?., 1993, 34, 5015 Ph Ph

OMe

78:22 (anti:syn) * dried under microwave condi~ons Texier-Boullet. F,; Latouche, R.; Hamelin, J. Tetrahedron Let?., 1993, 34, 2123

m. .

P,; Pastor,A.; Vilaplana, M.J. Tetrahedron Lett., 1993, 34, 3773

1. Na+ NHS02Tol,60°C THF/DMSO, 19h ) M~~Npha~ -0Ac 2.03, NaOH/MeOH -78OC, 3h Jumnah, R.; Williams. J.M.J, Tetrahedron L&t., 1993, 34, 6619

90%) Et2N+ +‘“‘, )

PhOqwt2

2. PhOH , NaOH , THF C8h7

C8h7

61% 30% Richardson, P.F.; Nelson, L.T.J.; Shamless.K.B. Tetrahedron Lett., 1995, 36, 9241

17

0

hv , PhSH ,2h

fl

N

..

(82

6:12) 66%

trans:cis Naito. T,; Honda,Y.; Miyata, 0.; Ninomiya, I. J. Chem. Sot., Perkin Trans. l., 1995, 19

SECTION 353: AMINE - HALIDE, SULFONATE Br2, CH2C12 0.5 MeOH * 0.01 Et3NHCl

Brr-(=)-NMe2 near quant.

Gervat, S.; Lbnel, E.; Barraud,J-Y.; Ratovelomanana. V, Tetrahedron Lett., 1993, 34, 2115 “Ni;?B” , H20,15OC ,30 min 72% “Ni2B” = Ni(OAc)2.4 HzO/NaBHd Seltzman. H.H,; Berrang, B.D. Tetrahedron Lett., 1993, 34, 3083

312


Section 354

CF3SiMe3 , THF Etw, 15h,rt

Felix, C.P.; Khatimi, N.; Laurent.


mco2Et 0

iPrOH,HCl(+rt+ CN

I H

Foley. L.H, Tetrahedron Lett., 1994, 35, 5989

96%

SECTION 354: AMINE - KETONE

C Rechsteiner, B.; Texier-Boullet,

+ ON I

t

0

microwave (300W) 3 min

UPh

\ 0I /

, SiO2

N-H

F.; j-bnelin.

O- Li+

0 TfO-

-78OC

+

89%

J, Tetrahedron Lett., 1993, 34, 5071

/rHF

*

*35%

23OC

F . Kiselyov, A.S.; &&QWS~ I,, J. Org. Chem., 1993, 58, 4476

hv ,9,10-dicyanoanthracene

Zhang, X.; Jung, Y.S.; -0. 1993, 34, 5239

P.S.: Fox. MA;

78% Martin, P.S.; Merkert, J. Tetrahedron Lett.,

Section 354

Amine - Ketone

313

hv*

c

Winkler. JD,; Siegel, M.G. Tetrahedron Lett., 1993, 34, 7697

2

Me

\

hv ,9,10dicyanoanthracene MeOH/MeCN

,,o*,Me

M fd ,\\-\

Bn

N\

Bn 23% at 73% conversion

TM .

Khim, SK.; Marianr,. PLS, Tetrahedron Lett., 1994, 35, 999

0

0

0

O

PhNH;! , PhH , reflux

-*

*

0

0

0

N I Ph

90% Adembri. G,; Celli, A.M.; Lampariello, L.R.; Scotton, M.; Sega, A. Tetrahedron L&t., 1994, 35,4023

\ CT NH2

I

N

/

1. PhCHO 2. TMSOTf , MeCN acetophenone

*

&q- THF , -78OC

Wegman, S.; Wiirthwein. E.U. Tetrahedron Lett., 1993, 34, 30;

0 N

PhCHO

M

+

cat. PdC12(PPh3)2 Me

\

K2C03

I (E+Z)

Ph in Toluene 10% 85% in DMF 72% 2% Filionini. L,; Gusmeroli, M.; Riva, R. Tetrahedron Lett., 1993, 34, 1643 0

OBu

1. LDA , -78°C THF + xylene

2. xylene , reflux ,4h b,tiHBu

moda.

+

&HBu

(99.5 : 0.5) 92% T,; Tats&i, S.; Shiraishi, Y.; Akasaka, M.; It& S. Tetrahedron L&t., 1993, 34, 3297 OMe OMe

1. BF3aEt2, 2. crc12

THF

3. ally1 bromide , rt P

4. 10% aq. Na2C03

Giammaruco, M.; Taddei. M,; Ulivi, P. Tetrahedron Lett., 1993, 34, 3635

65%

Section 356

Amine - AIkene

N3

317

EtO$Y@‘t-

1. PPh3

+

2

%@Et

l

C02Et

Et02

C02Et

am-

EtO$

Y

92%

0

Palacios.F,; Perezde Heredia, I.; RubiaIes,G. Tetrahedron Lett., 1993, 34,4377

. -K.;

.

Kaneko, M.; Yajima, T. Tetrahedron L&t., 1993, 34, 4841 h

Bu$nH , AIBN ,O.O5M (syringe pump) ,2h

NHPh

h +

*

pi

/

PA

Phvv

SePh

45%

23% Refvik, M.D. Tetrahedron Lett., 1993, 34,490l

Schvvan.;

Me$\ (CH20)n, p-tsOHaH20 MeCN ,6Q*C

67-69% (64-67%ee) 4’J4Hb,,*,

Bn\

-

$

Bn

H Castro, P.; Ovem

J&;

Zhang, X.; &briano, P.S, Tetrahedron Lett., 1993, 34, 5243 t-BuNH2, MS 3A, 2h CH2C12,22*C

*

P

Merrr,,, t-B

94%

Sigman, M.S.; Eaton. B.E, Tetrahedron Lett., 1993, 34, 5367

t-Bu H

318


Section 356

Pb

l.LDA.THF

78% de1 Pozo Losada, C.; Olano, B. Tetrahedron Lett., 1993,34, 5497

Barluenu;

Bi/BuflBr

, MeCN

PON-Pb -Br

Bbuyan, P.J.; Prajapati, D.; Sandhu, JS, Tetrahedron Lett., 1993, 34, 7975

N Cb

, toluene , bv I

2

CH20Et

2.23OC, 12b 3. TBAF

N

\

N c

d N \ CH20Et

91%

Knapp. S,; Albaneze, J.; Schwar, H.J,J. Org. Chem., 1993, 58, 997

(66

..

34)

I Bn

Pb

Bebolz, L.G.; Stille, J,R, J. Org. Chem., 1993, 58, 5095 Phi , Pd(PPh& K2CO3 DMF , 70°C NHBn Davies, I.W.; Scopes, D.I.C.; Gallagher, T. Synlett, 1993, 85

99%

Section 356

Amine - Alkene

319

SnBu3 Bn\

.I

;;IJJTY

yHBn+

p-Me

. (17 Coldham. I, J. Chem. Sot., Perkin Trans. I., 1993, 1275

83) 65%

l

Leurs, S.; Vanderbulcke-Coyette,B.; Viehe, H.G. Bull. Sot. Chim. Be&., 1993, 102, 645

V9:nzBr3

NHPh

DMF

*

PhL

Jin, S.-J.; Araki, S.; Butsunan. Y. Bull. Chem. Sot. Jpn., 1993, 66, 1528

N

/

SEt

Bn A

w H

AlC13, CH&

, rt

voms NHBn

OTBS

84%

SEt

\r 77% Tohyama, Y.; Tanino, K.; Kuwajima. I, J. Org. Chem., 1994, 59, 518 I

4 w

NHTs

Br ’

5% Pd(OAc);!

N 10%P(o-Tol)3 , Na2CQ I -Ko Ts 88% 2 Bu@Cl ,9O”C, Id Larock. RC,; Yang, H.; Weinreb. S.M,; Herr, R.J. J. Org. Chem., 1994, 59, 4172

320

Com~n~um


Bernard-Henriet, C.; Grimaldi, J.R.; Hatem.

Section 356

NHNMe2 89% Tetrahedron Mt., 1994, 35, 3699

N I

..

(2.7 pearsOn. W&;

Me 1) 65%

1

Jacobs, V.A. Tetrahedron Lett., 1994, 35, 7001 PhNHOl-l , FeC12/FeC13 72% *

Srivastava, R.S.; Nicholas,.M.

w

NHPh

tetrahedron Lett., 1994, 35, 8739

dco2t-Bu

L

C7Hl

LDA Ahman, J.; &&&j.

P,J, Am. Chem. Sot., 1994, 116, 9781

Ph-NW

1. Ni(cod);! , MeCN Br

45% 2.16 NaBH4,6 MeOH

Sol& D.; Cancho, Y.; Llebaria, A.; Moret6, J.M.; Del&ado. A, J. Am. Chem. Sot., 1994, 116, 12133

Amine - Alkene

Section 356

321

1% (PCy3)g12Ru=CHCH=CPh2 wPhH , eflux ,6h a &I 86%

‘\OAc Kinoshita, A.; Mori. Synlett, 1994, 1020

\ - OAc -

-C-JO Fisher. GB,; Lee, L.; Klettke, F.W. Synth. Commun., 1994, 24, 1541 Ph Zn(Cu) , MeOH, H20, rt

\ /N\e . m.

Br

ultrasound

&, Jolie, R.; De Smaele,D. J. Chem. SE Chem. Cajun.,

1994,

53% 1221

Ph C02t-Bu

fN

/

LDA , TI-F , -78OC -n-

T

N I H

C02t-Bu

63% Coldham. I.; Collis, A.J.; MouId, R.J.; Rathmell, R.E. Tetrahedron Lett., 1995, 36, 3557

1

Et2N HNEt2, 20% Et3NHI, THF 10%Pd(dba)z,2 PPh3 65OC,

c7-h

b

18h

+

C7Ht

i J 70% (96:4 E.-z)

Besson,L.; Go&, J.; Gazes.


322


Section 356

C@Me Tf

4

NaCH(C02Me)2,5% Pd(PPh& LiCl , DMSO , 60°C

\

C02Me *

N Bn’

Vieart, N.: Gazes,B.; m C3H7

N

jBn

A v

53%

Bn’ Tetra~dron

Lett., 1995, 36, 50 15

ether, -5OOC-+ -1OOC,4h

Ph

*

F== C3H7

Ph

Ph

Proi/Ti

OiPr

Gao, Y.; Harada,K.; Usato, F. Tetrahedron Lett., 1995, 36, 5913 Ph Bu+i’--@ *

phi

15% Yb(OTf), , CH$12, rt N\ HN\ Ph Ph Bellucci, C.; Cozzi, P.G&;Umani-Ronchi, A, Tetrahedron Lett., 1995, 36, 7289 1. ~~~~~~ ph-NPh

NHPh

, Me$iCl

2. aq.NH@ 96%

Wang, D.-K.; Dai. L.-X.: Hou. X.-L, Tetrahedron L&t., 1995, 36, 8649 Ph2P

Ph2P

b

\I

Ph w--h3

w-h3

(8

cc;&3 l .

1) 80%

(5:1 cis: tranws)

Didiuk, M.T.; Morken, J.P.; fioveysla. A& J. Am. Chem. Sot., 1995, I1 7, 7273

56%

Ester- Ester

Section 357

323

13F3*OEt2, 210°C ,2h w

Br Ph~

5 eq m~~huline , lOO*C 10 eq. H20, 2d

SECTION 357: ESTER - ESTER

~~~~H f AIBN , TuI reflux ,2h

*

0 Ph ; Kee, I.S. Te?~~~e~~~~Lett., 1993, 34,4213

2. Hfl 3. p-TsOH , toluene

Shimada, S.; Tohno, I.; Hashimoto, Y.;

*. 8) 85~ (92 Chem. Lett., 1993, 1117

324

Section 357


r

l/50 CoC12 ,42h *

r

OH

OCHO

DME , 02, 80°C

Li, P.; Alter.

H, Can. J. Chem., 1993, 0 C02Me

K

acetone, SmI2 , THF 4% Fe(dbm)3 , reflux

C02Me 74%

CO2Me

-b Imamoto. T,; Hatajima, T.; Yoshizawa, T. Tetrahedron L&t., 1994, 3.5, 7805 Mf30

OTMS

I Pd(PPh3)4, TlOAc OMe , HF reflux , Id 89% T,; Kondo, Y.; Masumoto, K.; Yamanaka, H. J. Chem. Sot., Perkin Trans. l.,

aoto. 1994,235

0

PhCHO , Cp2Sn(thf)2 0-

To1 , O°C + 25OC

-

A(&()‘ph

Takano, M.; Kikuchi, S.; Morita, K.; Nishiyama, Y .; m.

77% Y. J. Org. Chem., 1995, 60, 4974

NaB0~4 H@ , Ac20, PhH Ph Nag03,55OC,

14h 67%

Bhat, S.; Ramesha, A.R.; Chandrasekaran. S, Synlett, 1995, 329 Also via Dicarboxylic Acids: Hydroxy-esters Diols

Section 312 (Carboxylic Acids - Carboxylic Acids) Section 327 (Alcohol - Ester) Section 323 (Alcohol - Alcohol)

325

Ester- Ether

section 358

SECTION 358: ESTER - ETHER, EPOXIDE, THIOETHER Bu$W-I , AIBN sPhH reflux ,6h, syringe asp t

Lee.;

Br Tae, J.S.; Lee, C.; Park, CM, T~tra~dr~n Lett., 1993, 34,4831 Me3

A

P

OH

@Me

1. CsF , M&N 2,

Meo2 k

92%

C02Me

Hojo, M.; Ohkuma, M.; Ishibashi, N.;

Tetrahedron Lett., 1993, 34, 5943 OTMS

0

(Tf~)2Sn(bis~~ine) w CH2C12,9h , -78OC

Ph

EtS I

PhCHO

86~ (93:7 ~~n:a~ti)

Kobayashi, S.; IJchiro, H.; Shiina, I.; Mukaiyama, T. Tetrahedron, 1993, 49, 1761 OzEt

1.3Bu$nH 0.25 AIBN C.X&Et 0.03M PhH reflux ,8h

54) 91% (46 ; Tae, J.S.; Chong, Y.H.; Park, Y.C.; Yun, M.; Kim, S. T~tra~~dr~n Let& 1994, 35, l

129

CCHO

ems ===c,40% sno SEt

*

20% Sn(OTf);! chiral diarnine slow addi~ou (3h) ; Kawasuji, T.; Mori, N. Chem. Let& 1994,217

SEt 61% (62% ee)

326

Section 359


COZMe Rhz(OA& , MeOH

49% Tet~a~d~~~ Lett., 1994, 35,

Cox, C.G.; Haigh, D.; Hind~~y, R.M.; Miller, D.J.; 3139

0 CP \ “_/“e

1. PhCHO , ZnC12 , CH2C12 , rt 2. CAN, MeOH, -78OC, CO

= Me0 Ph

oc T~trahed~~~ Lett., 1994, 35, 7889

Jiang, S.;

~cl2-AgPF6, MeO$

COzMe

CH$&

CO,n/le

=

MeOH

*

MeO$Z

f==c

C02Me

quant. Kataoka, Y.; Ma~umot~, 0.; Ohashi, M.; Yamagata, T.; Tani. K, Chem Lett., 1994, 1283

SECTION 359: ESTER - HALIDE, SULFONATE [CF2Br$Z#n, DMF ,2h, rt] HMPA , CuBr , 60°C, 40 min *

98% 0

0 Mawson, S.D.; Weavers. R,T, Tetrahedron Let& 1993, 34, 3139

HoqoH

3HBb~~,lhh_

Bc

= S

= r:

=: =

= =

$H

&H

XAc

XAC

2.2 MeCOBr , dioxane ) 16h

/

80% El Anzi, A.; Benazza, M.; Frechou, C,; Demaillv, C, Tetrahedron Lett., 1993, 34, 3741

Br

Ekter- Halide

Section 359

327

s

CHzC12,18h m-

cCO2H

his-(sym-collidine) iodine(I) hex~~ophosphate Simonot, B.; Rousseau G, J. Org. Chem.,1993, 58,4

76% I

89%

Kitagawa, 0.; Inoue, T.; Hirano, K.; muchi.

T, J. Org. Cbem.,1993, 58, 3106

IQ, sodium persulfate, NaHC03 HOD Royer, AC.; Mebane, R.C.; Swafford, A.M. SynZett, 1993, 899

0

BzCl ,0.4 SmI3, MeCN , rt t

BzO/-\I

0

Yu, Y.; m.

87% Y,; Ling, R. Synth. Commun., 1993, 23, 1973

*c

I

1. HC=CC02H, NC1 , CH2C12 2. (BzO), , PhH, eflux

Haaima,G.; Lunch, M.-J.; Routledge,A.; Wu

0

78~44%

0

Tetrahedron, 1993,49,4229

ICH2C@Et, DMSO BEt3, rt (opento air)

C02Et -

T

; Mu~gl~, E. Tetr~~~~r~~ Left., 1994, 35, 2763

I

54%

328


BQ\ #

y-CO2H

H

1. mcpba

Section 359

ONlb2

2.12, NaHC03 50%

Reetz. MT,; Lauterbach,E.H. Heterocycles, 1993, 35, 627 Me

b.

X,; Wang, 2.; Ji, J. Tetrahedron Lett., 1994, 35, 613

Mimero, P.; Saluzzo, C.; m.

R, Tetrahedron Lett., 1996, 35, 1553

BeIIesia, F.; Boni, M.; Ghelfi. F,; Pagnoni, U.M. Tetrahedron L&t., 1994, 35, 2961 FzBr

Bu$nH , AIBN, PhH

t reflux , l-15 h addition ~ Meat ButtIe, L.A.; Motherwell. W.B, Tetrahedron Lett., 1994, 35, 3995 MeOg

Section 359

Ester - Halide

329

0 A Buoys

ma

c1

TBAB 190°C ) 6h S 97% K~ey~~

A.; Kiyota, M.;

Ph Y

0

T~tr~~~drun L&t., 1994, 35, 4571 Cl

AcCI , Cp2YCI w CH2C12, 13h

AcO ~

Ph

..

(88 ; Zhu, I), ~ynt~. ~~~~~.~

Cl

+

AC

Ph 12) 95%

1994, 24, 2203

I2 , Pb(OAc)za3 Hz0 , AcOH wrt ,6h 85% Bedekar, A.V.; Nair, K.B.; S~rn~n. R, ~ynt~. ~u~~~n., 1994,24, 2299 Br

PhMe3Nf Brf Ir Br

; G&in, R.H.; Musket,

GM.; Aionso, M.S. Tetr~~edrun, 1994, 50, 6433

Cl

Pimmg, F.O.H.; 1994,50, 12415

0.3 Cu(~py)C~ , DCE

57% (70:30) ; Kaptein, B.; Schoemaker, H.E. Tet~~~dr~~~


330

00

, Zn , ether

0 w

25OC, 18h

Cl

Section 360

PhK

,/\/\/c’ 70%

Bhar, S.; &nu. BC, J. Org. Chem., 1995, 60, 745 SECTION

360: ESTER - KETONE 0 55%

1. Br

OH

Ktr

Br Py, ether Cd-f23 53% 2. TMSCl , ether cl lH23 Zn , reflux Landi Jr., J.J.; Garafalo, L.M.; &.mig. K, Tetrahedron Lett., 1993, 34, 277 COzMe

2% Rh2[02CCH(Bn)NPhth]4 C02Me

CO2Me CH2C12,O°C

d-

3S S bh

96%

(46%ee, R) Hashimoto, S.; Watanabe,N.; Sato,T.; Shiro, M.; Ikegami. S, Tetrahedron Lett., 1993, 34,

5109

x

Ph

1.7 PhI(OH)OTs , CDC13

-A rt ,2h 98% CO2Et C02Et Barton, D.H.R.: Jaszberenyi.J.Cs,; Shinada,T. Tetrahedron Lett., 1993, 34, 7191 PhCHO , EtN02 AlC13, 100°C, 5h

Sartori. (i; Bigi, E.; Maggi, R.; Bemardi, G.L. Tetrahedron Lett., 1993, 34, 7339

331

Ester - Ketone

section 360

Br

PhL

l-

, csgo3,

CH$& C02Et

48h, 30°C 2. aq. HCI, CHCI3 , Him-da, Y.; unhip,;

Tanaka, Y,; Ueda, I. J. Org. ~~~.,

1994, 59, 111

1. (Coa)2 , hv t

60%

2. MeOI-I

02Me ; Hardee, J.R.; Gelber, N.; Qi, L.; Axenmd, T. J. Org. Cbem., 1994, 59, 2131

ICI-I ) THF ,18-c-6 , rt

Me

4

60%

0

AC

Ph JL

OAc ,4% Pd(P~h3)2C12

Cl

w C7Hl K

SnBu3

Ph C7Hl

8% CuCN ,75”C, 18h

~

J, Am. Cam. Sot., 1994, 116, 1

Ye, J.; Bhatt, R.K.;

N c1

Ph -If

0

CO&B u

0

0

IsJr&o. B, Te&hedron

96%

L&t., 1994, 35, 5073

74%

0

332

Section 360


Me

Me

Mn(OAc), , AcOH 8O”C, 8h w

Me02C

0

C02Me 57%

C.-P,; Wang, S.-F. Tetrahedron Lett., 1994, 35, 4365 1, NaH , DME ,40°C 2. BuLi 3. PCC , Al203 , CHg12 93x68x68% Piers. E,; Cook, K.L.; Rogers, C. Tetrahedron Lett., 1994, 35, 8573 0 KMn04, CuSO&

Hz0 47%

4h * Das, J.; w

0

c

0

S, Tetrahedron, 1994, 50, 11709 e- , CH2C12- Hz0 NaBBr2

C02Me

C02Me 87%

Maekawa, H.; Ishino, Y.; mguchi. OH PhI-

L Chem. L&t., 1994, 1017

aq. t-B&OH, C02Et

1% CuC12,3% TBAB

CH2C12, 25OC, Id

*

PhA

C02Et 96%

Feldberg, L.; Sasson. Y, J. Chem. Sot. Chem. Commun., 1994, 1807

Section 360

Ester=Ketone

333

68% Ryu, 1; Nagahara,I(.; Yamazdci, H.; Tsunoi, S.; Sonoda. N, Synlett, 1994, 643

Bu$nH, AIBN

(9

m,

Kinter, KS. J. Org. Chem.,1995, 60, 4850 OCQMe

Barba, I?.-

e’ , DMF/LiCIOd

0

67% h&G.: Montero. Cr..I. Org. Chem.,1995, 60, 5658 KMn04, pH 7 OEt

Tat‘iock. J,& J. org. Ckm, 1995,

C02t-B u

60,

OEt 0 97%

6221

1. CuBr2, PhI(OH)OTs , 0°C 2. DMAP .,dimethyldioxirane CH2C12,O”C

0 C@t-Bu 0

1st stepis quant Coats, S.J.; Wasserman.H.H, Tetrahedron Lett., 1995, 36, 7735

OPh

1.

J-I-IF

Li

PhCHO w;

Section 361

Com~n~um of Organic Synthetic Means, VoI 9

334

oAc

88~78%

2. p-TSA , A&H, 90°C , ld * PhA/ Yang, 2.; Moutou, J.-L. Tetrahedron Lett., 1995, 36, 841

l

--c Br

0

SmI2, THF , -35*C, 5 min

0

4 0

0

72%

d Park, H.S.; Lee, I.S.; I(im. YK


REVIEW:

“Alternate PreparationsOf aXeto EstersFrom Acid Chlorides,” &&i&&y. A,&; Wang, 2.; Wells, A.P. Org. Prep. Proceed. Int., 1995, 27, 457 AIso via ISetoacids Hydroxyketones

Section320 (Carboxylic Acid - Ketone) Section330 (Alcohol - Ketone)

SECTION 361: ESTER - NITRILE OAc I phwCHO

Nc Pdz(dba)&HQ , dppe MeCN, Id

Nemoto, H.; Kubota, Y.; Yamamoto. Y cJ. Chem. Sot. Chem. Commun., 1994, 1665

TBAF,THF,lh LiCI , rt

94% CN

Stojanova, D.S.; Milenkov, B.; Hesse.M, Helv. Chim. Acta, 1993, 76, 2303

Ester- Alkene

Section 362

335

ESTER - ALKENE

SECTION 362:

This sectioncontains synthesesof enol estersand estersof unsaturatedacidsas well asester moleculesbearing a remotealkenyl unit. 0

C02H

1. Br2, NaHC03 2. AgNOj , AcOH

Bu

Bu 66x50%

J&,&

T&; Huang, J. Tetrahedron Lett., 1993, 34, 1411 1. &CO3 ,5 kbar 2.5% Pd(OAc)z , 10% P(2-furyl)3

Jco2H

61%

3. HC=CCMe20Ac, DMSO 20°C , 14h ** Bouyssi, D.; Gore, J.; BaIme, G.; Louis, D.; Wallach, J. Tetrahedron L&t., 1993, 34, 3129 Me

90% Ciattini, P.G.; Mastropietro, G.; Morera, E.; Ortar, G, Tetrahedron Lett., 1993, 34, 3763

Ph-C=CH , NEt3, MeCN , rt 0 PdC12(PPh3)2 , CuI , 1Oh

*

Cu. X,; Huang, X.; Ma, S. Tetrahedron Lett., 1993, 34, 5963

Me$iCH=C=O , PhH OSiMe3

reflux ,3d

Me$iO Ito, T.; WT...

.

. ..

Me& T, Tetrahedron Lett., 1993, 34, 6583

P Ph

80% (>97:3 z:E)

336


\a

C@Me

Section 362

PBn C@Me

I

MeN02, 80°C

0

65%

A

OBn

&lark& I.&; Evans, G.R. Tetrahedron tett., 1993, 34, 7309

c

Co-Cl2 C@Me

(30

Me0 Et

..

70) 29% [60:40 E:zJ

Bhatia, B.; Reddy, M.M.; Iabal.

@Et

Tetrahedron L&t., 1993, 34,630l

1. SnC12 / 2.

=c_ ut.

CI-IO ,ether,rt >

F,; Gabriel, A.; Maillard, B.; Pereyre, M. Tetrahedron Lett., 1993, 34, 7749 cw

w bock.

5% Pd(OAc)z ,2 NaOAc DMSO , O2 )

am0

86%

RC,; Hightower, T.R. J. Org. Chem., 1993, 58, 5298 Bn

AcHN -A

1. PhSeCH$H20H, cw

Weinhouse, ML; Janda.

EDC

DMAP , DMF 2. Hz@, THF 3. iPr$H , CHCl3, reflux Synthesis, 1993, 8 1

Bn w AcHN

A

04 92x90%

Section 362

Ester - Alkene

337

+h\

cCO2H

DMSO , Na2CO3 28-46h

70% Tetrahedron L&t., 1993, 34, 8545

Annby. U,; Stenkula, M.; -C.-M.

30%

;Jmco2Et

PPh3 7PhH , rt ,8h

Guo, C.; Lu.

.I. Chem. Sot. Chem. Commun., 1993, 394 Et0

OMe

CO2Me

,O.S Bu$nH E tog-

41% doMe

Lee. E,; Hur, CU.; I&e, 1466

,0.05 AIBN , reflux ,4h PhH (0.01 M) , syringe* pump v(2h)

C02Me Y.H.; Park, Y.C.; Kim, S.Y. .I. Chem. Sot. Chem. Commun., 1993,

P(OEt)3 , NEtyH20

,120OC -

C02Et

-COzEt

8h (sealed tube) 96%

Hirao. T,; Hiraw

K.; Ohshiro. Y, Bull. Chem.

TIN,

SOC.

Jpn., 1993, 66, 2781

MeOH,3MHCl 3-26h

Me0 Me0 Thakkar, K.; Cushman, M, Tetrahedron Lett., 1994, 35,644l

Section 362


338

Pd(OAc)z , dppp , PhMe , MeOH w COzMe reflux

Mand;u. TJ Tsujiguchi, Y.; Tsuji, J.; Saito, S. Tetrahedron Lett., 1994, 35, 5701 Bu [Pd(MeCN)2(p&)d @=I12 co, THE;, 5o”c (10 Kg cms2)

‘b O

0

+Bux; 2

.

83) 92% Y, Tetrahedron Lett., ;994, 35, 5889

(17

Matsushita, K.; Komori, T.; Oi, S.; w.

l.NaI-I,TMEDA,THF,reflux 2. inverse addition to PhOCOCl

0a

OPh 43%

Harwood, L.M.; Houminer, Y.; Manage, A.; Seeman.J-1,Tetrahedron Lett., 1994, 35, 8027

eC02Me PhCHO

*

phL-oH

34%

DABCO , microwave, 10 min CO2Me Kundu, M.K.; Mulcherjee, S.B.; Balu, N.; Padmakumar,R.; I$&& S.V,Synlett, 1994,444 BrCHzCOfle , Bu3As , 10% Cd PhCHO

100°C ,20h

Zheng, J.; ahen, Y, Synth. Commun., 1994, 24, 2069

*

PhwC02Me 87% (E only)

Nz

\)I

339

Ester - Alkene

Section 362

Lf Rh2(s-TBSP)4

CO2Me

p-(t-butyl)phenylsulfonyl prolinate 76% (63% ee) . TBSP = Peng, ava; Z-Q.; Houser, J.H. Tetrahedron Lett., 1994, 35, 8939 Mac

,3.5% Pd(OAc)z 8% PPh3 , 1.2 Ag2CQ , MeCN 90°C, 45 min 80%

Meyer, F.E.; Ang, K.H.; Stenig, A.G.; de Meijere, A. Synlett, 1994, 191 -0Ac

, CO, THF , autoclave

RuC12(PPh3)3-K2C03, 2OOOC, 77%

Kondo, T.; Kodoi, K.; Mitsudo, T.-u.; Watanabe.Y t J. Chem. Sot. Chem. Comnun., 1994, 755

1. Rieke Mg* , THF , rt 2. ethylene oxide ) THF , -78OC v

a

3.co;!,o”c + rt 4. H30+, 1lOC

Rieke. R.D; Sell, MS.; Xiong, H. J. Org. Chem., 1995, 60, 5143 Me0

nBu3 SPh

cu(No3)2

Ph

9m 9fi

CO2Me 65%

-

TV

CO2Me SPh Beddoes,R.L.; Cheeseright,T.; Wang, J.; Quayle. P, Tetrahedron Lett., 1995, 36, 283

340

Compendiumof Organic Synthetic Methods,Vo19

Section 362

COzMe Ph3A

CO2Me

4

SePh

PhCHO

*

CHC13,4h Huang, Z.-Z.; Huane,

4

SePh Y. -7* Tetrahedron Lett., 1995, 36,425

.

-F C3H7

96% (90:10, Z-E)

PhH

w7

Ph

I

5% ClzPd(PPh3h.4 NEt3 20atmC0,PhH,l10°C,10h

0

99%

Cop&et, C.; Sugihara, T.; Wu, G.; Shimoyama,I.; Negishi. E, J. Am. Chem. Sot., 1995, 117, 3422 -cl

; NEI+;IH2C12,-20°C

a *

.

0

w.

.

OBn 75%

G,; De Simone, A.; Mingardi, A.; Tomasini, C. Synlett, 1995, 1131

3) 95%

(>97

Zhu, G.; Lu. X, Tetrahedron Asymmetry, 1995, 6, 345 m PhO

Cl

SiMe3 , toluene AlC13, 20°C ,2h

-

PhOL 82%

Mayr. H,; Gabriel, A.O.; Schumacher,R. Liebigs Ann. Chem., 1995, 1583

Section 363

osMe3

OPl

. m.

341

Ether - Ether

M+C

-

COzMe

zrC14,Cc4,0°c

~

pflzc

+ rt

Mew . &, Sudoh, T.; Koyama, K. Bull. Chem. Sot. J’n., 1995,68, 1683 RelatedMethods: Also via Acetylenic Esters: Alkenyl Acids: P-Hydroxy-esters:

SECTION 363:

80%

Section60A (Protectionof Aldehydes). Section 180A (Protectionof Ketones). Section 306 (Alkyne - Ester). Section322 (Carboxylic Acid - Alkene). Section 327 (Alcohol - Ester).

ETHER, EPOXIDE, THIOETHER EPOXIDE, THIOETHER

- ETHER,

SeeSection60A (Protectionof Aldehydes)and Section 180A (Protectionof Ketones)for reactionsinvolving formation of Acetalsand Ketals. 1. DDQ , MeOH , CH2C12 rt, Id 2. aq. NaHC03 OMe &I. Y.-C,; Lebeau,E.; Gillard, J.W.; Attardo, G. Tetrahedron L&t., 1993, 34, 3841

4 /

H

iPrOH ,20% CuC12 5% Pd(N0)2C1(MeCN)2 2h

50% isolated Meulemans,T.M.; Kiers, N.H.; FeringZLR.L; van Leeuwen, P.W.N.M. Tetrahedron L&t., 1994, 35, 455

HO

DEAD, PPh3, CHg12, O°C HO OH

80% @-only) Sobti, A.; Sulikowski. G.A, Tetrahedron L&t., 1994, 35, 3661

78%

Section 364


342

(a$ = 1:15) 81% BTIB = his-(trifluoroacetoxy)idobenzene Sun, L.; Li, P.; Zhao. K, Tetrahedron Lett., 1994, 35, 7147 TMS-SPh , DMF w

‘OMe ;w”l

Miura, T.; w.

0

87%

Y, Tetrahedron Lett., 1994, 35, 7961 OSiMqt-Bu Q = 2 s\

OMe

t

ZnI2 , THF

p-To1

70% (>99% e) Kita. Y,; Shibata, N.; Fukui, S.; Fujita, S. Tetrahedron Lett., 1994, 3.5, 9733

ETHER, EPOXIDE, THIOETHER SULFONATE

SECTION 364:

1. ClCH21, MeLi , -78°C ‘Ls 2. -78OC +

+20°c

Br Barluenu;

- HALIDE,

Me4N*#,,,, ,,\+,Me 62% $

Cl

Llavona, L.; Bemad, P.L.; Concellbn, J.M. Tetrahedron Lett., 1993, 34, 3173 H

XeF2

, CH2C12,35OC

Stavber, S.; Zupan, M. Tetrahedron Lett., 1993, 34,4355

Section 364

Ether - Halide

343

MnO2, AcCl w Cl 82% Bellesia, F.; Ghelfi, F.; Pagnoni, U.M.; Pinetti. A, GQzz.Chim. Ital., 1993, 123, 289

t(

OMe

OMe

Br2, Me&Cl, NaBr ,30 min B *

OMe

3-(

OMe 98%

Bell&a, F.; Boni, M.; Ghelfi.;

Pagnoni, U.M. Gazz. Chim. Ital., 1993, 123, 629

60% Antonioletti, R.; Magnanti, S.; Screttri, A. Tetrahedron Lett., 1994, 35, 2619 l.LDA,HMPA 2. acetone 3. X2,NaHC03

32x47% Galatsis. P,; Parks,D.J. Tetrahedron L&t., 1994, 35, 6611 H ,,OH @9

,,\\I”\l\

12, NaHC03 , dry MeCN

IIIIIIIIB u

Bu 16h 04

*

d-J

r,e % -1

75% Barks, J.M.; Knight. D.W,; Weingarten, G.G. J. Chem. Sot. Chem. Commun., 1994, 719 PhI(&~F3)2

9t t 12 cc14

D’Auria, M.; Mauriello, G. Tetrahedron Lett., 1995, 36,4883

83% I

Section 365


344

AK13 , Id

.

(4 s

1) 60%

J.0,; Biermann, U. Bull. Sot. Chim. Be&., 1994, 10, 393

CT I

(collidine)$ PFi t

\A/\/\

0

CH2Cl2

95%

Brunel, Y .; Rousseau,G. Synlett, 1995, 323

&

12, CAN, MeOH *

rt ,2h

I*

+

I

.

I\

1) 88% (2 6 ; Hosokawa,H.; Kanamori, M.; Muramatsu, Y.; bhiai, K.; Takahashi,E. Chem. Lett., 1995, 13 .

.

SECTION

365:

ETHER,

EPOXIDE,

THIOETHER

- KETONE Me

‘OSiMe3

0

OH

BFpOEt2, MeN02, -25OC 30 min

?Y-

51%

(7:3 syn:anti)

Duhamel. P,; Guillemont, J.; Poirier, J.-M. Tetrahedron Lett., 1993, 34, 4197 2% Cu(hfacac)z, CH2C12 40%

reflux *

c

hfacac = hexafluoroacetyl acetonate Clark. J.S; Krowiak, S.A.; Street,L.J. Tetrahedron Lett., 1993, 34,4385

\

Section 365

Ether - Ketone

345

%

M

2Me:3Me) I

I 0

M&, Rivera-Fortin, M.A.; Byrne, N.E. Tetrahedron Lett., 1993, 34, 3505 Ph, t-Bu

, Me2AICl

A-

,,,,,d Ph

SPh

CH2C12,-45OC

(96:4) where 4 = other isomers Horiguchi, Y.; Suehiro, I.; Sasaki,A.; Kuwaiima, I, Tetrahedron Lett., 1993, 34, 6077 Me Me

TMS zc

I cf

5% TMSN(S02F)2 CH2C12,-78OC

Trehan, A.; Vij, A.; Walia, M.; Kaur, G.; Veu.. 7335

0

p-TsOH , H20, CH& 20°C, 12h Cossy. J,; Furet, N. Tetrahedron Lett., 1993, 34, 7755

&r

. Treh;iB. S, Tetrahedron Lett., 1993, 34,

*

SePh 70%

346

Section 365


5

[mCl(C2H4)d

2 9 SnC12

acetone, Ar , 80°C

P

sealedtube, 1Oh

-* Tetrahedron Let?., 1993, 34, 7971

Ipatkin, V.V.; Kovalev, I.P.; Ignatenko, A.V.; Nikishin.,

C02Me TrSbC16,CH$12 ,-78’C (>2OO:1)

76%

Colander. GA; Cameron,K.O. J. Org. Chem., 1993, 58, 5931

M%* ,,+ (‘I

Al(OC&)3 , toluene O°C,2h

0

) o2

%

Me Ishihm, K.; Han&i, N.; Yamamoto, H. Synlett, 1993, 127 w-h1

0

= Z = Z

Me

Me

Me

>99% (86:14 S:R)

63% Groth, U,; Huhn, T.; Richter, N. Liebigs Ann. Chem., 1993, 49 OH MeCHO , PhSH , CH-& SiO2 , rt Fuchs, K.; m.

I&

J. Org. Chem., 1994, 59, 528

SPh

Section 365

Ether - Ketone

347

OEt C5Hdy 66%

O

PCWP = peroxotungstophosphate Sakaguchi,S.; Watase,S.; Katayama,Y.; Sakata,Y.; Nishiyama, Y.; I&ii. Y c.I. Org. Chem., 1994, 59, 5681 N-NHCO$t

7/

Me

1. Br2 3. 2. MeOH, NaHC03H+ 4. H30+

*

+

0

5. DBU 77%

Feuerer, A.; Sevea T, J. Org. Chem., 1994, 59, 6026 Ph k== TMSO

3 eq. SnC4, -78OC,CH$l;! *

PhbSPh

67% m.

k; Michael, J.P.; Walter, D.S. Tetrahedron Let&, 1994, 35, 5481 (~-To~)~S~, cat. Ph2CO , Yb rt ,3h

. . Tanlguchl. Y,; Maruo, M.; mi.

STolyl IL; Fuiiwara. Y, Tetrahedron Lett., 1994, 35, 7789

KF-Al203 , t-B&OH, Pha ~v.K.;

Ph

0 CH2C12

MeCN , 10 min

Ph

5, PhI>K 0

quant

Kapoor, K.K. Tetrahedron Lett., 1994, 35,948l 0

1. NBS, (BzO)2, CC4, heat 56% +

2.1.5 Ag2C03 , MeOH , heat

Me0 . Cl m. N,; Stanoeva,E.; Boeykens,M. Synthesis, 1994,427

OMe


348

Section 365

1. EtCH(OMe)z , TiCL4 ;~lz,-780C,lh

EtzNqms2

.

2

quant. 0 Hojo, M.; Nagoyoshi, M.; Fujii, A.; Yanagi, T.; Ishibashi, N.; Miura, K.; Hosomi. A, Own. Lett., 1994, 719

OH

W-h

2

4

OAc

9 CH2Cl2

2 snCl;!,2 NCS , -1O’C 80% (40x50synxznti) Masuyama. Y,; Kobayashi, Y.; Kurusu, Y. J. Chem. Sot. Chem. Commun., 1994, 1123

4f

CO2Me

3e4*

>

. .

82%

G,; Zhang, Y.; Dreyer, G. Tetrahedron Lett., 1993, 34, 449 1 PhMezSiH , hexane, rt OSiMQPh

0 o=

(PPh3)rnH

*

Chan. T.H,; Zheng, G.2, Tetrahedron Lett., 1993, 34, 3095

(t

/ 84%

351

Ether - Alkene

Section 367

/a Pd(PEW4

0 9 W03

9 DMF

60°C , 1.5h \

66%

OMe

4\/

OMe

Arcadi, A.; Cacchi. S;&qock. R.C.; Marinelli, F. Tetrahedron Lett., 1993, 34, 2813 OMe w

9rt OMe I

PhCHO 0.5% Yb(fod)3

addition of K2CO3preventsformation of this Deaton, M.V.; Ciufolini. M.A, Tetrahedron Lett., 1993, 34, 2409 TM

TM 1. iBuMgBr , cat. Cp2TiC12

~TBS

70% Tani, IS.; Sato, Y.; Okamoto, S.; Sate. F, Tetrahedron Lett., 1993, 34, 4977

r(i

Me H

+

1. OSM LiC104, ether 2.1N HCl , THF 15 min, 0°C t

\

NHBoC

6

OTBDMS (8: 1 threo:erythro)

. PA,; Moher, E.D. Tetrahedron Lett., 1993, 34, 5567

-YOEt OEt

1. Me2S , TMSOTf , -78OC * 2. PhSLi

-yoEt

J&I. S,; Park, J.H.; Lee, J.M. Tetrahedron Lett., 1993, 34, 5769

91% SPh


352

x

Section 367

OMe OMe

b

,0.3 p-TsOH

neat, rt

Bn

71%

prlohr. P, Tetrahedron Lett., 1993, 34, 6251

g

y;~p;~s

Semmelhack.ML&; Epa, W.R. Tetrahedron Lett., 1993, 34, 7205

F3

Ph aPh

SEt

+ Ph CF3

Nti,rt,2h

I.3

(94:6 Z:E)

Beg&, J.-P.; Bonnet-Delpon, D.; M’Bida, A. Tetrahedron Z&t., 1993, 34, 7753

cf

OMe OMe

OMe TMSOf , iPr2NEt -2OOC + rt ,4h

Gassman.P.G.; Bums, S.J.; Pfister, K.B. J. Org. Chem., 1993, 58, 1449 SMe

II

1. catecholborane , 3% PdClz/dppf

2* phnBr

, reflux

aq. NaOH ,2h Gridnev, I.D.; Mivaura. N.: Suzuki. A,J. Org. Chem., 1993, 58, 5351

62%

Section 367

Ether - Alkene

‘*Me3siJcc1 , BF3.()Etzw c6H 13CHO

2. DBU/LiClO&leCN , 60°C

Wl

D’AnieUo, F.; Mattii, D.; Taddei. M, Synlett, 1993, 119

Ph#‘CH$H$IH

, &CO3

PhCl , heat Billeret, D.; Blondeau, D.; Sliwa.

MeCN

~y~the~~~,1993, 881

e,

52%

==c

2. NaOMe , heat

ue.

,OMe

1. MeOH, HCl,, , ether O°C,5d

OMe

Joglekar, B.R, Synth. ~u~~~~., 1993, 23, 1979

, PhH ) 100°C

Bu

3c Bu

sealedtube 6Me

62% ’

Harvey. D.F,; Neil, D.A. Tet~uhedr~n~ 1993,49, 2145

Ji, J.; b. X, .I. Chem. SW. Chem. Comun.,

0

1993, 764

NaOCl , Mn(salen) cat. 45% (64% ee)

\ I ether f 4-Ph-p~dine-N~xide Chang, S.; Heid, R.M.; bobsen. E.W, Tetruhedr~~ Lett., 1994, 35,669 Ph-C&H , PhH , 90°C ph/\s-+ AIBN , sealedtube Ph 2h 23% 65 Benati, L.; Capella, L.; Montevecchi, PC; Spagno~o,P. .I. Org. Chew., 1994, 59, 2818 Ph\/SH

354


Section 367

Lee, G.H.; Choi, E.B.; Lee. E.: Bak. C,S, Tetrahedron L&t., 1994, 35, 2195 PhSH , Pd(OAc);! THF,50°C,14h

*

72%

Backvall. J.-E,; Ericsson, A. J. Org. Chem., 1994, 59, 5850 Br

-+

Ph

C02Me

CR-

Ph Ni(C0)4, MeCN , MeOH

76% (80:20 cis:trans)

Ni(C0)4, TlOAc , MeOH 66% (30:70 cis:trans) Llebaria, A.; Camps,F.; Moreto, J.M. Tetrahedron Lett., 1994, 35, 4011

De-A,:

HO

= Iz TMSOTf , CHg12, -76OC HO :ee = OH i)H 94% 94% (>99:1 a$) Toshima. IK; Ishizuka, T.; Matsuo, G.; Nakata,M. Tetrahedron Lett., 1994, 35, 5673 SPh +

CuOTf , PhH/THF ,25OC, 0.3 h

SPh

SPh an alternative to cuBreMe$ &hen. TJ Shook, C.; Thiruvazhi, M. Tetrahedron Lett., 1994, 3.5, 6041

mez.

SPh 99% SPh

ijc, :.:g::** 0 G,; Figadere,B.; Cl&y, P. Tetrahedron Lett., 1994, 35, 6295

Section 367

355

Ether - Alkene

1.2 q. ZuEt2 , cat. Ni(acac);?, THF 2.CuCNe2LiCl

Vaupel, A.; Knochel,.

T~trah~d$~n Lett., 1994, 35, 8349

PhSLi , LiC1 , Pd(PPh3)4

*

OTf

SPh

Tl-IF , reflux 89% A.G; Barciua, LO.; Cerezo,A. de F.; Su~r~~ian, I&R. ~y~~e~~, 1994, 561 1. HZrCp2Cl , THF 25OC, lh c6b-+==

2.

cx 0

Pereira, S.; Zheng, B.; &&m&J&J.

Cl’

*

Z-02

0, 0 wl3

76%

Org. Chem.,1995, 60, 6260

CpzTiMe2, THF ,65OC OMe

OMe 67% Petasis.N.A,; Lu, S.-P. Tetrahedron Lett., 1995, 36, 2393 M!vlPP , MeOH, rt

MMPP = mouoperoxyphthalatehexahydrate TYAnnibale, A.; Scettri. A, Tetrahedron L&t., 1995, 36,4659

YmrsoJc

91%

ems *

Ph

SnClz-AcCl , CH$$ ,4h 66% yama. T,; Ishiwata, A.; Sam, T.; Matsuda,T.; Takahashi,M.; Koga, G. Tetrahedron Let& 1995, 36, 5581

Section 368

Com~n~um of Organic Synthetic Methods, Vol9

356

S

W(OAr)(OPr)(CHCMe3)Cl(OEt)2 5c

ms-

quant.

0

Leconte, M.; Pagano,S.; Mutch, A.; Lefebvre, F.; met. 132, 1069

J.M Bull. Sot. Chim. Fr., 1995,

Section 18OA(Protectionof Ketones)

RelatedMethods:

HALJDE, SULFONATE - HALIDE, SULFONATE

SECTION 368:

H~~ycloprop~a~ons are found in Section74F (Alkyds from Alkenes). Cl&XC13 , toluene ,3h mph Sakai,;

Cl,&Ph 41% RuC12(PPh)3)3 , 120°C2, Sugimoto, K.; Shigeizumi, S.; Kondo, K. Tetrahedron L&t., 1994, 35, 737 1. Cl2 , NF3*OEt2

Cl

N-OH

-0

82%

2. HCI

Cl

Tordeux, M,; Boumi~e, K.; Whelp.

0

NOH

C,J. Org. Chem., 1993, 58, 1939 F

NO’BFi , PPHF

80% F

* (>< PPHF = pyridinium polyhydrogen fluoride York, C.; Prakash,G.K.S.; Wang, Q.; Olah. G.A,Synlett, 1994, 425

0I

Br

C l&XMe3Mn04 , Me3SiBr * CH2C12,O*C

Hazra. B.(lli; Chordia, M.D.; Bahule, B.B.; Pore, VS.; Basu, S. J. them. Sot., ~erkin Trays. l., 1994, 1667 /,

KIC12, Hfi )

Ph -I

/--Cl

/+--I +

Ph \

I 1) 94% _Zefirov.NS,; Sereda,G.A.; Sosonuk, S.E.; Zyk, N.V.; Likhomanova, T.I. Synthesis, 1995, 1359 Cl

(6

.

Section 369

Halide - Ketone

SECTION 369:

357

HALIDE, SULFONATE - KETONE 0

Cl hexane, rt

d

N I

92%

Cl

de Faria, A.R.; Matos, C.R.; Correia. C.R.D, Tetrahedron Let?., 1993, 34, 27 NBS , aq. MeCN , cat. HCI C02Et

rt ,6h

-

Br-C02Et 81%

-ton.

H.E.; Leanna, M.R. Tetrahedron Let?., 1993, 34,448l

1. ClCH21, MeLi , -78OC 2. MesSiCl , -78OC-+ rt

TMS

Et Cl

OEt * + Br Br Barluenm. J,; Pedregal,B.; Concellon, J.M. Tetrahedron Let?., 1993, 34,4563 OH Br 0

83%

HTIB ,12, MeCN , r-t; reflux ,20h F

HTIB = hydroxy p-tosyloxyiodo benzene

Bovonsombat, P.; &lcN&s. L Tetrahedron, 1993, 49, 1525 1. pyridinium polyhydrogen fluoride ‘O-c=)-’

2. :;;c,,, 3. &CO3

*

‘={rx--

61% Karam, 0.; Jacauesv.J.-C,; Jouannetaud,M.-P. Tetrahedron Let?., 1994, 35, 2541 Ph

1. PhCHO ,5% (BiC13*1.5ZnCl2) Ph y-y” zc 2. Me$iCl 0 Cl Le Roux, C.; Gaspard-Iloughmane,H.; Dubac. J, J. Org. Chem., 1994, 59, 2238

>88%

358

0 II ph/SvF

1.2 LDA ) THXWMPA ) -78°C 2. CgH1qcHU c

0 F

3. FVP (5~8OC) Reutrakul, V&; Kruahong, T.; Pohmakotr,M. Te~r~~e~~o~ Lett., 1994, 35,4853

82~48%

~~*~z,~Hz~~z rt , overnight 49% conversion Bovonsombat,P.; Angara, G.J.; McNelis. L Tetrahedron Mt., 1994, 35, 6787

NBS Yt-BuOH ) 30°C 1.5h

54%

,,

Coss~=J; Furet, N, ~~t~~~edru~ ~tt.~ 1995, 36, 3691 1. HZZrCp;1Cl 2. A&l, 15%CUB~~SM~~ w

3. NBS

Br C6h3

+

93%

zheng, B.; ~rebnik. M, Tet ra hed ran Lett., ~995~ 36, 5665

2.2 eq. FeCf3) DMF

fl;

”

-4m

Thompson, D.F. J, Chem,Sot., &&in Trans. -I., 1995, 23 15

f-j

Section 371

Halide - Nitrile

359

0 DMSO , (CoC1)2 t MeOH 93%

0 NEt3 , CH2C12, -6OT Raina, S.; w.

*

~

Cl

V.EL. Tetrahedron, 3995, 51, 2467 Ff12-HCO,H ,

30-lS*C ,2h * F

70% Chambers, R.D.; Greenhall, M.P.; Hutchinson, J. J. Chem. Sot. Chem. Conmun., 1995, 21

SECTION 370:

SLIDE,

SULFONATE - NITR~E

NO ADDITIONAL

SECTION 371:

EXAMPLES

HALIDE, SULFONATE - ALKENE 1. LDA 2. CIP(O)(OEt)2 0

I 3. TMS-I

Lee, K.; Wiemer. D.F, Tetrahedron Let?., 1993, 34, 2433

LDA , ether

Br Shino~u~, H.; ~

~t~oto.

K, Tetrahedron Let?,, 1993, 3#,4985

1. C13CCN 2.12 ) &CO3, ether b-

+ H

76% x 88% 7h5 C7H15

(33 Friesen. R-W,; Giroux, A.; Cook, K.L. Tetrahedron Let?., 1993, 34, i983

83%

360


Section 372

85% O- F.-T,; Kumar, KA.; Hsieh, L.-C.; Wmg, R.-T. Tetrahedron Lett., 1994, 35, 2553

cat. Pd(OAc)z ‘ILiCl a+ G benz~uinone , 20°C $ t AcOH-acetone IBackvall. J.-E&;Nilsson, Y.I.M.; Andersson,P.G.; Gatti, R.G.P.; Wu, J. Tetrahedron Lett., 1994, 35, 5713 0

0

Iz,CAN,MeCN,5h reflux

I 55% (67/33 dlkwso)

6

C6h3

SiMe3

IPy2 BF4/2HBF4 , CH2C12

I

C6hJ

w

-

w

77% ~~~~~n~~ J,; ~v~ezaG~c~a, L.J.; Gonz~ex, J.M. Tetrahedron Lett., 1995, 36,2153

1. ICI, CH2C12, -78OC 2. NaOMe , -78OC

*

I/n/wll

43%

reversing order of ad~tion leadsto 38% of Z-iodoalkene Stewart, SK.; ~ SECTION

C3H-7

372:

CHO


KETONE

- KETONE

AC@, CoCJ2

MeCN Bhatia, B.; Punniyamurthy, T.; -1.

* C3H~~c~7

+

0 15% J, J. Org. Chem., 1993, 58, 55 18

C3H7~cH3

61%

0

361

Ketone- Ketone

Section 372

2 PhLi, THF , 20°C

30 min

eswff.

2

Ph

Ph

95%

*

-R0 UT,; Zhou, M. Tetrahedron Lett., 1993, 34, 571

Ph

P+MgBr THF , -7OOC

60%

RJtL; Iyer, V.S. Tetrahedron Lett., 1993, 34, 3683

OTMS

Bn

kc

9 Fq(W9 CO, ether I 2h

0 Zhou, T.; Green. J.R, Tetrahedron Lett., 1993, 34,4497

Ph

ph~oH

, DMF , O°C Mn(pic)s /

Ph Iwasawa, N.; Hayakawa,S.; Funahashi,M.; Isobe, K.; Narasaka. K, Bull. Chem. SOC.Jpn. 1993, 66, 819

Mohr, B.; Enkelmann, V.; Wegner. G, J. Org. Chem., 1994, 59, 635

Section 373

Com~n~um of Organic Synthetic Means, Vol9

362

OTMS

J

a

OTMS

*

0

BFs*OEtz

61%

J, Org. Chem, 1994, 59, 1485

Jenkins, T.J.; Burnell.,

0

0

Yb-TMS-Br 68%

THF , reflux I

K

Tanigychi. Y,; Nakahashi,M.; Kuno, T.; Tsuno, M.; Makioka, Y.; Takaki. K.: Fuiiwara. Y, Tetrahedron Lett., 1994, 35,411l OAc

Maikap, G.C.; Reddy, M.M.; Mu~opadhyay, M.; Bhatia, B.; &b&& 9145

Tetrahedron, 1994, 50,

H PCWP, DCE , reflux ,3h Bu

Bu + OH

mp

= bC5fkN(CH2)15Md3

Iwahama, T.; Sakaguchi,S.; Nishiy~a, Y.; m.

93% (~4~(0)(02)2bl 0 Y, T~tr~hedr~~ Lett., 1995, 36, 1523

REVIEW:

“a-Diones from Cyclic Oxamidesand ~g~o~i~iurn Reagents:A New, Generaland Environmentahy Beneficial Synthetic Method,” ~r=West~. UT,; Zhou, M. ~y~Ze~, 1994,975

SECTION 373:

KETONE

- NITRILE

, DCE ,70aC t 20% Pd(OAc)2nPPh3-dppb 65h LL Org. ~he~.~ 1994, 5%2679 Nozaki, IS.; Sato, N.; ma.

Ph

Phe

0

74%

Section 374

SECTION

Ketone- Alkene

374:

KETONE

363

- ALKENE

For the oxidation of allylic alcohols to alkeneketones,seeSection 168 (Ketones from Alcohols and Phenols) For the oxidation of allylic methylenegroups (C=C-CH2 + C=C-C=O), see Section 170 (Ketonesfrom Alkyls andMe~ylenes). For the ~yla~on of alkeneketones,also seeSection 177 (Ketonesfrom Ketones)and for conjugatea~ylations seeSection74E (Alkyls form Alkenes).

4 Meo2cer-o

PdC12(PhCN)2) 50°C SnC12,MeCN y33h Masuvam~ Y,; Sakai,T.; Kurusu, Y. Te~r~~e~~~~ L.&t., 1993, 34,653 OCO2Me

Das, N.B.; Sarma,J.C.; Sharma. R.P,; Bordoloi, M. Tetrahedron Lett., 1993, 34, 869

w

SnBu3

)

AIBN

m.

G.A.; Andersh, B.; Su, Q.; Shi, J. Tetrahedron Lett., 1993, 34, 1741 P 1.

wm5 ?== Me0 50°C ,3h, SiO2

2. CAN, O.lM aq. HNO3 rt, 20 tin Harrity, J.P.A.; Kerr, W.J,; Middlemiss, I>. Tetrahedron Lett., 1993, 34, 2995

86%

364

Com~n~um

&

C02Et


Section 374

1. PhH , Cu(OAc)2@2H@ Pb(OAc), ,2d

CO2Et

2. ethylene glycol , CH2C12

\

* & Schultz, A.G.; Holoboski, M.A. Tetrahedron Lett., 1993, 34, 3021

MI-O, CHfl12, rt t

-+*,,,w

SiOdA1203

MT0 = methyltrioxorhenium Junga, H.; Blechert. S. Tetrahedron Lett., 1993, 34, 3731

Mo(C0)6 , DMSO , Toluene 100°C ,12h Jeonrr. NJ Lee, S.J.; Lee, B.Y.; ~hung, Y.K. Tetrahedron Lett., 1993, 34,4027

Br

Yu, Y.; Lin, R.; m.

SmIy,THF,rt,2h 02N*cHo

*

p~No2

Y, Tetrahedron Lett., 3993, 34, 4547

CHCl3 , rt ,8h

TBDMSA

TBDMS

Konopelski. J.P,; Kasar, R.A. Tetrahedron Lett., 1993, 34, 4587

78OC

Section 374

Ketone - Alkene

365

BufinH , AIBN, 60°C syringe pump (3h) ,O.O2M

Rawal. VH,; Zhong, H.M. Tetrahedron Lett., 1993, 34, 5197

Bu3s-YoEt I Bu 3SwOEt

hJL hJL

n

OEt

OEt P 0.01 PdCl2(MeCN)2, 20°C 75% * * DMF ,2h OEt Par-rain, J.-L.; Beaudet, I.; Duchene, A.; Watrelot, S.; Quintard, J.-P. Tetrahedron Lett., 1993, 34, 5445 P

Cl

FLke2

CF$E 88%

CH2C12, reflux ,96h Ales, C.; Janousek, 2.; Viehe. H.G. Tetrahedron Lett., 1993, 34, 5711

CF?

1. BuMgBr , 10% CuI, TMSCl HMPA , THF , -78OC 2. CH212 ,2 eq. Et2Zn

biker-Milbum.

))

c

3.2.2 eq. FeC13 , DMF , O°C - B+3=099x93x54% 4. NaOAc , MeOH M.1,;Thompson, D.F. Tetrahedron Lett., 1993, 34, 7291

slzN&$ fast addition

(2:l z:E) 70% Sha. C.-K,; Shen, C.-Y.; Jean, T.-S.; Chiu, R.-T.; Tseng, W.-H. Tetrahedron L&t., 1993, 34, 7641

366

m;

Com~n~um of ~g~ic

Syn~e~c Means, Vol9

Section 374

Kassir, J.M.; Semones,M.A.; Weing~en~ M.D. T~~~~~~~r~~L&t., 1993, 347853

; Riesinger, S.W, J, Org. Cafe,, 1993, 58, 408

Me

11

.*

\

27)

~7%

Ihle, NC.; Heathcock. CH, J, Org. Gwen., 1993, 58, 560

( Ew~2zn EtQgz

II

Bu CuBrGMe2, HMPA TMSCl

C02Et 65%

C~mmins. M.T,; ~~te~et, P,XX; Trotter, B.W.; Vatlin, I.M.; Watson,P.S.; McKerlie, L.A. Reinhold, T.L.; Cheung, A.W.; Stetson,K.A.; Dedcpoulou, D.; Gray, J,L. J, Org. Chem., 1993, 58, 1038

Section 374

Ketone - Alkene

367

0

0

53%

2.2 eq, CuSO4, llO°C Trost. B.M; Parquette, J.R. J. Org. Clef.,

1993, 58, 1579

co2(c0)8, MeCN rt -9 75OC

91% *

Me

0

Hove. T.R,; Suriano, J.A. J. Org. Chem., 1993, 58, 1659

2 eq. PhCHO , ZrOC&8 IT20

Ph 73%

Yuki, T.; Hashimoto, M.; Nishiyama, Y.; Ishii. Y,J. Org. Chem., 1993, 58, 4497

Ph

z=z=

Ph Ph

5% Pd(OAc)z ,4 NaOAc 100°C, DMF , BQNCI 84%

Ph

Larock, R,C; Doty, M.J.; Cacchi, S. J. Org. Chem., 1993, 58, 4579 0

Bu

W(CO)6, THF , CO, sealed tube BU

hv ,65OC j,

llO°C

J. Am. Chem. SW., 1993, 115, 1154

0

Co~~n~u~

368

TMS

of Organic Syn~e~c Mean,

PhC=CH , S&14-NBu3

w

~ l .

-A.;

I

Section 374

Vo19

Ph

~ 85% (203 Ez)

’ Hirarna, M. J. Am. Chem. Sot., 1993, 115, 3362

0 In--f

0 Ph

5% RhCl(PPh3)3,toluene , 120°C

Ph *

3 huffs,

~ 84%

M.A.; ~,ie~eskind. L.S, J. Am, ~~~~* Sm., 1993, 115, 4895 Me$KN Cp2Ti(PMe&

Berk, S.C.; Grossman,R.B.; Buchwald. S.L,J. Am. Chenz. Sm., 1993, 115, 4912 COzMe

CO, 10% Pd(OAc)z-dppp Phi-MeC~-MeOH

r

&&U&N. T,; Tsuji, J.; Tsujiguchi, Y.; S;zito. S, J. Am. Chem, Sm., 1993,

TiC14, CHg12, -40°C, lh

81% 0 115,

5865

C02Et

OMe funk. I?J& Fingered, J.F.; Olmst~ad,T.A,; Para, KS,; Wos, LA. J. Am. Clef. Sot,, 1993, 115,8849

Ketone- AIkene

Section 374

I B”

II

~

369

, 10% (c~)CpRuCI OH

20% NH4PF6, neat, 1OOOC

Bu

B-M,; Martinez, J.A.; Kulawiec, R.J.; Indolese, A.F. J. Am. Clef. Sot., 1993, 115, 0

PhCHO ) SnCIz , Na2SO3

Br Ph~ Lin, R.; Yu, Y.; Zhang Y, Wyatt, C~~~~.,

-

PhTPh

73%

0

1993, 23, 271

tduene , sealedtube ,23”C -+ 50°C

Srikrishna. A,; Krishnan, K.; Van Kateswarlu, S. J. Chem.Sm. Chem. Coals.,

&

1, D;ue

1993, 143

, SnQ- Bu3N

70%

~~

Ph auchi. MJ Sehata,M.; Hayashi, A.; Hirama, M. J. Chem.Sot. Chem. Comnzun.,1993,

Bu’-\-(

PPh3, EtOH , PhH 0

reflux

72%

0

Guo, C.; Lu. X, J. ~~~. Sm., Pe~~~~Trans. I., 1993, 1921 +gb+%-

SePh

SnBug

AIBN , toluene

Watanabe,Y.; Yoneda, T,; Okumura, T.; Ueno, Y.; Tom T, Butt. Chem.Sm. Jpn., 1993, 66, 3030

370


Section 374

H

0

0.01 mol dmB3 toluene , reflux

b&&&u&;

a I-f

-~

0 53% Takada,K.; Odagaki, Y,; hoe. S, .I. Chem. Sot. Chem. Commun., 1993, 556

l

0 2. 3. 1. BuGnOSnBu3 PhCHO H20 , (-C02) , HMPA 0 Nishio, M.; Baba, A.; Mats&a, H. Chem. Lett., 1993, 1219

%0 mT.:

62%

t

1. Me&I , CHQ , rt ,30 min 2. PdC&(MeCN)2,9h

4

SiPh3

siPh3

w

/

64%

Degl’Innocenti, A.; Capperucci,A.; Bartoletti, L.; Mordini, A.; Reginato,G. Tetrahedron Lett., 1994, 35, 2081

CM% 6

~seo2H~p~~~

~OH

+ ~

leq.,rt,14h 35% 2 eq., 20°C, 14h 20% 2 eq. , reflux ,2h Barton. D.H.R; Wang, T.-L. Tetrahedron Lett., 1994, 35, 5149

36% 75%

90%

Li

0

Ph~

e(

me2

OEt

*

Ph j;r

enolate free a-alkoxy vinyllithium reagent improved prep & procedure Shimano, M.; Meye;rs.AJ, Tetrahedron Lett., I994, 35, 7727

OEt 90%

Section 374

Ketone- Alkene

371

I

C5Hll

TMSCl , MeCN , rt ,3h Me -c

I o. F.-T,; Hsieh, L.-C. Tetrahedron Lett., 1994, 35, 9585

3% co2(co)fj

co,

EtOg

w

3, DME , Id

92%

0

Eto

EtO?C 82%

Jeong. N,; Hwang, S.H.; Lee, Y.; Chung, Y.K. J. Am. Chem. Sot., 1994, 116, 3159 Ph CpzTi(PMe& , Schlenk tube Me$iCN , PhH 80%

Berk. S.C,; Grossman,R.B.; Buchwald. SL, J. Am. Chem. Sot., 1994, 116, 8593 NHMe Meu

1. PhMgCl , CeC13, -78OC, THF * 2.10% AcOH

Me

MYYMe Ph

0 85%

Bartoli. Cr,;Cimarelli, C.; Marcantoni, E.; Palmieri, G.; Petrini. M, J. Chem. Sot. Chem. Commun., 1994,715 I!!7

0

0

3. 1.MeCH(Cl)SPh KH CO2Me

2.ZnCl2

4. DABCO

c!b Amecke, R.; Groth. I J,; Kohler, T. Liebigs Ann. Chem., 1994, 891 MST J= C3H7

*

90x88%

TiCI4 , LiAlH4, CC4 CHEt

C3H +

f4=i

Mitani. M,; Kabayashi, Y. Bull. Chem. Sot. Jpn., 1994, 67, 284

63% (2)

Cl

Et

Section 374


372

16 /l/I

,rt,3min Sn@HMPA

2.MeOH,rt,3min 3.0.1 N aq. HCl , rt 3 min

.

(9

1) 84%

Miyoshi, N.; Takeuchi. S,; Ohgo, Y. Bull. Chem. Sot. Jpn., 1994, 67, 445 PhCHO , Ni(cod)zPPh3, Zn

*

ph-Y 52% OAc 0 Masuyama. Y ,; Sakai, T.; Kato, T.; Kurusu, Y. Bull. Chem. Sot. Jpn., 1994, 67, 2265 dioxane ,6O*C, 4d

0

2 eq. Mn(OAc)s , Cu(OA& * AcOH ,8O*C

c

CD 0

52%

er. B&; Cole, B.M. J. Org. Chem., 1995, 60, 5376

C -I.;

t-BuMe$iH , Rh4CO) 12 CO, PhH , reflux 14%

63% Ishibashi, H.; Ii, N. Tetrahedron Lett., 1995, 36, 241 0

0 A

x

co(co)4

NaH **

X=NHTs X can also be OH, CHNO2, C(CO2Me)z Bates. R.W,; Devi, T.R. Tetrahedron Lett., 1995, 36, 509

X=NTs,69%

Section 374

Ketone- AIkene

373

2.25 CAN, DMF , O°C, 1.75h

F-vans.P.&, Longmire, KM.; Modi, D.P. Tetrahedron Lett., 1995, 36, 3985 0 e’ , clots 81% -

SiMe3 Chueh, L.L.; Tsay, S.-C.; fIwe

Lin.; .,,c7c15

C02Et

4

SiMe3

Tetrahedron Lett., 1995, 36,4093

PPh3m-hul~

,“,“,”

I toluene

ylyco2Et #

82% SaW, M.K.E.; j?elIicciari. R, Tetrahedron Lett., 1995, 36, 4497

Resek,J.E.; Mevers. A& Tetrahedron Lett., 1995, 36, 7051 OMOM EtO$-

ZnI

Me$iCl , CuCN , HMPA EtO$~;

l

.

68%

Huang, S.; Guise, L.E.; Lacy, D.B. Tetrahedron Lat., 1995, 36, 7061 0

Ph-Bt Bt = benzotriazole

1. BuLi * 2. cyclohexanone, ZnBr2, toluene llO°C, 12h c

60% Katritzkv. A.R,; Xie, L.; Toader, D.; Serdyuk, L, .I. Am. Chem. Sot., 1995, 117, 12015

Ph

374


iPrNO2, DBU , MeCN

Section 375

4

65%

rt ,4h

Balllnl.,

Bosica, G. Tetrahedron, 1995, 51,4213

78%

Bates, R.W,; Rama-Devi, T.; Ko, H.-H. Tetrahedron, 1995, 51, 12939

8% MeReO3, C13CCF3

reflux ,5d 80%

Schneider,M.F.; Junga, H.; Blechert. S, Tetrahedron, 1995, 51, 13003 Ph Ph

=

Ph

, toluene ,135OC

WH)2(CW’P~3)3 7lh

85% (9:l)

Kakiuchi, F.; Yamamoto, Y.; Chatani, N.; Murai. S, Chem. Lett., 1995, 681

SECTION 375:

NITRILE - NITRILE NO ADDITIONAL EXAMPLES

375

Nitrile - Alkene

Section 376

NITRILE

SECTION 376:

- ALKENE

l.LDA,THF, 3 eq. HMPA , -78OC

phTCN

2. Me1 , -78OC

NMePh

*

,mcN

81%

NMePh

Me 100% z

Chang, C-J.; Farm, J.-M,; Liao, L.-F. J. Org. Chem., 1993, 58, 1754 I. PPh3, PhH ,rt PhhN3 I Ph

2. Ph$=C=O , PhH , rt

51% Molina. P,; Alajarb, M.; Lbpez-Leonardo, C.; AlcGntara, J. Tetrahedron, 1993, 49, 5153 1. Me$iCH2MgCl,

THF , -2OOC 36%

2. PC13, THF ,67OC so. H.-E, Gilbert, B.A.; Hwu, JR. J, Check Sot. Clef.

C~~~n.~

1993,669

2 LiCN ,0.07 Pd(PPh3)4 0.07 12-crown-4

UTf

CN

PhH,rt Piers. E,; Fleming, F.F. Can. J. Chem., 1993, 71, 1867 CN Cl

/==-c

CN

0

CN

c.3

MezN=CClz Cl, CH$& 2 eq. NEt3 , -15*c

Cl *

Me2N

+

79% Bouvy, D.; Janousek, 2.; Viehe, H.G. ~~~2,Sot. Chum. Belg., 1993, 102, 129

Yamamoto. Y;, Al-Masum, M.; Asao, N. J. Am. Chem. SM., 1994, 116, 6019

CN

Section 377

Cum~n~um of Organic Synthetic Methods, VoI 9

376

1. Pd&dba)3eCHC13 , 10h

Me

a 2. /y/Pr

,4%CuI,2eq.~,D~

PdCI(PPh3)~CH~h), rrt ,4h Suginome,M.; Kinugasa, H.; Ito. Y, ~e~r~~e~r~~Lett., 1994, 3.5, 8635

Et02C\/CN

-CHO

, TfQT

* *co2Et 6% RuH2(PPh3)4 83% b ur&&hi. . S. I.: Naota, T.; Taki, H.; Mizuno, M.; Takaya, H.; Komiya. S,; Mizuho, Ye; Oyasato, N.; Hiraoka, M.; Hirano, M.; Fukuoka, A. J. Am. Chem. Sot., 1995, 117, 12436 Ph-

KCN , DIvIF , NiBr2(PPh3)2 * Zn , PPh3, 50°C

Br

PhwcN

99% (95f5 En) Sakakibara,Y.; Enami, H.; Ogawa, H.; Fujimoto, S.; Kato, H.; Kunitake, K.; &saki. K,; Sal& M. Bull. Chem. Sot. Jpn., 1995, 68, 3 137

SECTION 377:

ALKENE

- ALKENE

1. (Me2N)+CHZ 4 eq. NaN(SiMe3)2

*

C13TiO 2. 5

eq.

c3

CHO

Reynolds, K.A.; Dopico, P.G.; Sunde~ann, ML; Hughes, K.A.; Finn. M,G,J. Org. Chem., 1993, 58, 1298 1. Cp2ClZra GoH21--CHO

SnBug

CH2C12 2. BF3*OEt2 Maeta, H.; Hasegawa,T.; &uki. M, Synlett, 1993, 341

D-

c a21

N

92% (96:4 EZ)

Alkene - Alkene

Section 377

377

Bu

OTIPS

Bu (cod)RuCpCl

mt.

..

11 R .W; Indolese, A. J. Am. Chem. Sot., 1993, I 1.5, 4361

4) 68%

Ph ,OPh (fp\

0 -20°C , lh

C7Hl 4 Yanagisawa, A.; Hibino, H.; Nomura, N.; Yamamoto. H, J. Am. Chem. Sot., 1993, IIS, 5879

ZnCl PdW’bh , m--n?,rt Mazal, C.; Ultier.

M, Tetrahedron Lett., 1994, 35, 3089

B” Bu

=

Bu 3. cat. CuCV2LiCl , hcl 50°C, lh

-

Bulc 87%

Takahashi. T,; Kotora, M.; Kasai, K.; Suzuki, N. Tetrahedron Lett., 1994, 35, 5685 Br 1. CjH llMgB , NiClz(dppe) , THF 2. PhMgBr , NiQ(dppe)

Ph

PhS/ W-h */ 52% Babudri, F.; Fiandanese,V.; Mazzone, L.; Naso, F, Tetrahedron Lett., 1994, 35, 8847

378


Br

$”

Section 377

Ph

, Pd(OAc)2, 10 kbar ,2d

PPh3, NEt3, TI-WMeCN , 20°C * c Voigt, K.; Schick, U.; Meyer, F.E.; de Meijere, A. Synlett, 1994, 189

0

Schmitz, C.; Harvey, J.N.; Viehe. H.G. Bull. Sot. Chim. Belg., 1994, 103, 105

(65 35) 91% Araki, S.; Imai, A.; Shimizu, K.; Yamada,M.; Mori, A.; Buts&an. Y,J. Org. Chem., 1995, 60, 1841

n

I

Pd(OAc)2, TPPTS aq. MeCN , iPr2NH 5

CO2Me P BU-

BuT 80%

C02Me

3

&O

Genet,J.P.; Linquist, A.; Blart, E.; Mouries, V.; Savignac,M.; Vaultier, M. Tetrahedron Lett., 1995, 36, 1443 COzEt lbleF$%~C6H13

Pd(OAc)2, PPh3,DMF ,28h rt , sealedtube Ph Matsuhashi, H.; Hatanaka,Y.; Kuroboshi, M.; Hivama. T, Tetrahedron Lett., 1995, 36, 1539

Section 377

Alkene - Alkene

379

Ph Yoshida, A.; Matsumoto, S.; Feng, IF.;Matsumoto, Y.; Sugino, A.; Hanamoto,T.;

. Mlkaml,; &

Tetrahedron

1995, 36,907

ktt.,

/

OSiMe3 d-

SiMe3 w

10%ZnClz , CH$& 25OC, L5h Ph

+ f I Ph

(22

.

78) 94%

Furuhashi, K.; Natsume,H. Tetrahedron L&t., ;995, 36, 5243

BT.;

I

Bu

Bu OH

, IXvlF:Hz(,

C3H+V

5% Cp~u(~)Cl

, loo°C

C3H7

st. B.M; Indolese, A.F.; Miiller, T.J.J.; Trepton, B. J. Am. Chem. Sot., 1995, 117, 615

Bu

ZZZ

Bu

1. Cp2ZrEt2 2. CHz=CHOEt

Bu

Bu w

3. H+

m

.

50%

T; Kondakov, D.Y.; Xi, 2.; Suzuki, N. J. Am. Chem. Sue., 1995, I1 7, 5871

380


Me$i

=

WoPh

Section 377

9 PMe3

w-h3 CPa-BU2

81% Suzuki, N.; Kondakov, D.Y.; Kageyama,M.; Kotora, M.; Ham, R.; Takahashi.T, Tetrahedron, 1995, 51, 4519 Ph 10% RhCl(PPh3)3,PhMe

*

110°C * 80% Wender. P.k; Takahashi, H.; Witulski, B. J. Am. Chem. Sot., 1995, 117, 4720 1. TaCl5 , Zn , DME , PhH 2. THF w-h-w11

3. -0

Li+

4. aq. NaOH 65% T.&G. K,; Yamada,M.; O&&a, H.; IJtimoto. K,; Fujii, T.; Furukawa. I, Chem. k-K 315

19%

1. :cc12 C6H1-TMs 2. CsF 9DMF * cald/ . . m. &; Kobayashi, Y.; Koyama, K. J. Chem. Sot., Perkin Trans. l., 1995, 653

(95

.

72%

5) 86%

Yanagisawa,A.; Hibino, 1-I.;Habaue,S.; Hisada,Y .; Yasue, K.; Yamamoto.H, Bull. Chem. Sot. Jpn., 1995, 68, 1263

381

Oxides - Alcohols

Section 380

OXIDES - ALKYNES

SECTION 378:

0 * piTo Leonine,

1.2eq. Bu$nC=CBu , DMF 2% Pd(MeCN&12 rt,30min

l

SECTION 379:

77%

J.A.; Ventura, M.P. Te~ra~edrun Let& 1993, 34, 3663

OXIDES - ACID DERIVATIVES NO ADDITIONAL EXAMPLES

SECTION 380:

OXIDES - ALCOHOLS, THIOLS

Domfnguez, E.; w.

J.C Tetrahedron Lett., 1993, 34, 5803

OEt / P-- OEt \

MePO(OEt)z, BuLi , THF BF3*OEt2,-78OC

0

Li, 2.; Racha, S.; Dan, L.; El-Subbagh, H.; Abushanab.

MeO-PhCHO

83%

J. Org. Chem.,1993, 58, 5779

R

P Me0

\

H

+ 10%Li binaphthalenide, TI-IF

Ph

Me&’ Me0v

98% (20% ee) OH

Rath, N.P.; Spillincr. C.D, Tetrahedron Lett., 1994, 35, 227 0

, SmI2,THF

S02Ph 71% Te~ra~edrun Lett., 1994, 35, 5441

382


Section 380

OH = E P

3.3 eq. La-Li-(R)-BJNOL complex MeNO*, THF , -40°C, 72h

CHO NPhTh

-+

NPhTh

NO2

99%

(99:l erythro:threo; 96% ee) N Tetrahedron Lett., 1994, 35, 6123

Sasai,H.; Kim, W.-S.; Suzuki, T.; wi.

l.LHMDS,O”C 2. PhCHO , 0°C 3. HCl , EtOH

92) 62% (8 VJ$.; Worrall, J.M.; Adams,H.; Alexander, R. Tekahedron Lett., 1994, 35, 6167

-al.

0

1. EtLi

0

0 t

P Ph’ II1Jk Ph

3.10% AcOH 2. CeC13, THF , -78OC

OH

P Ph’ II14 Ph

Et

71% Bartoli. G,; Sambri, L.; Marcantoni, E.; Petrini, M. Tetrahedron Lett., 1994, 35, 8453 vyOH

H202

OH . . ovicelll.

; w.

.

9 TS-1

4oH * 0

TS-1 = metal dopedzeolite

quant. P,; Sanetti, A.; Mincione, E. Tetrahedron Lett., 1994, 35, 8477 Ph S02Ph 1.2BuLi,THF

# Ph

2. t-B&OH, 15h -7OOC+ 2o”c 90% (55:45 erythro:threo)

Chemla, F.; Julia. M; Uguen, D. Bull. Sot. Chim. Fr., 1994, 131, 639

Section 383

Oxides - Amines

383

Bakers yeastI 4h

tiNo2

74% (99% ee , S)

uama. A,; Occhiato, E.G.; Spinetti, L.M.; Vallecchi, M.E.; Scaarpi, D. Tetrahedron, 1995, 51, 1775

SECTION 381:

OXIDES - ALDEHYDES CO/H2 (600 psi) , CH2C12 98%

Totland,K.; A,lpgr. )t J. Org. Chem., 1993, 58, 3326

SECTION 382:

OXIDES - AMIDES M BnNH2, NaH ,2.5h

9R 99

) TolO$ NHBn Me%,,, TolO$ + 82% * Cl Satoh, T.; Motohashi, S.; Kimura, S.; Tokutake, N.; Yamakawa, K, Tetrahedron Lett., 1993, 34,4823 1. CAN, MeCN , NaN02, Id 2. Hz0

NO2

64% NHAc Reddy, M.V.R.; Mehrotra, B.; Vankar. Y,D, Tetrahedron Lett., 1995, 36,486l

SECTION 383:

OXIDES - AMINES

,CO,Me Nw

p-TolS02SePh AIBN , PhH reflux

Brumwell, J.E.; Simpkins. N.S.; Terrett, N.K. Tetrahedron L&t., 1993, 34, 1215

Section 384


P\

C3HW

OEt

95°C) neat, 6Oh

Ruder. S.M; Norwood, B.K. ~e~r~~e~r~~ Lett.,

1994, 35, 3473

X

X NO2

\ I

bakers yeast, 4d

m

/

kv

NO2

NH2

\

+

I

/I

Q NO2

No,

3) 37% X = Et (1 1) 36% X = OMe (5 Davey, CL.; Powell, L.W.; Turner. NJ,; Wells, A. Tetr~h~d~o~ L-e& ~99~, 35, 7867 l

. l

N-Tr

NHTr = =

[La, BINOL , Li] , THF =c dp

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods

Compendium of Organic Synthetic Methods