Compendium of Organic Synthetic Methods
Compendium of Organic Synthetic Methods Volume 8 MICHAEL 6. SMITH DEPARTMENT OF CHEMISTRY
THE UNIVERSITY OF CONNECTICUT STORRS, CONNECTICUT
A Wiley-lnterscience Publication
JOHN WILEY 81 SONS, INC. NewYork
Chichester
Brisbane
Toronto
Singapore
Cover illustration was adapted from "Disconnect By the Numbers: A Beginner's Guide to Synthesis" by M. B. Smith. Journal of Chemical Educetion, 1980, 67, 848-856.
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@
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DEDlCAT10N This book is dedicated to Dr. Ted Hoffman, who recently retired as Senior Editor at Wiley-lnterscience after a long and distinguished career. Ted was responsible for getting the Compendium started and for keeping it going for more than twenty years. The many books and series for which Ted served as editor have contributed enormously both to chemical education and to chemical research. It would be difficult to find a bookshelf in an organic chemistry research lab anywhere in the world that does not contain one or more of the books for which Ted served as editor. On a more personal level, the publication of Volume 6 of this series in 1988 began my career as an author, and many new opportunities have been opened to me because of this. There are certainly many others who can similarly thank Ted. Iwant to use this dedication to thank Ted for his help to me, for his help to the previous authors of the Compendium, and for his contributions to the chemistry community in general (particularly the organic chemistry community). Those contributions are many and important. Thank you, and good luck in your retirement. MICHAEL 6. SMITH
V
PREFACE Since theoriginal volume in thisseries by Ian and Shuyen Harrison, thegoal of the Compendium of Organic Synthetic Methods was to facilitate the search for functional group transformations in the original literature of Organic Chemistry. In Volume 2, difunctional compounds were added and this compilation was continued by Louis Hegedus and Leroy Wade for Volume3 of theseries. Wade becametheauthor forVolume4 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 Section 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 8, contains both functional group transformations and carbon-carbon bond forming reactions from the literature appearing in the years 1990, 1991, and 1992. The classification schemes used for Volumes 6 and 7 have been continued. Difunctional compounds appear in Chapter 16.Theexperienced user of the Compendium will require no special instructions for the use of Volume 8. Author citations and the Author Index have been continued as in Volumes 6 and 7. 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 E-mail addresses given below. Note that the phone and fax area code for this section of Connecticut is tentatively scheduled to change in 1996 to (860). The manuscript for Volume 8 was prepared on a Macintosh-llciTMPC using Microsoft Word” (version 5.1) for word processing. All structures were prepared using ChemDraw” (version 3.1)and the manuscript was printed with a Laserwriter” II printer. The graph presented in the introduction was prepared using Cricket-Graph.”
vii
viii
PREFACE
As I have throughout mywriting career, 1 want to thank my wife Sarah and my son Steven, who have shown unfailing patienceand devotion during this work. I also thank Ms. Carla Fjerstad, who edited this volume and was responsible for its publication. MICHAEL B. SMITH
University of Connecticut Department of Chemistry 215 Glenbrook Rd., Room 151 Storrs, CT USA 06269-3060 Voice Phone: 203-486-2881 Fax: 203-486-2981 E-mail:
[email protected] CONTENTS ABBREVIATIONS INDEX, MONOFUNCTIONAL CO APO J IDS INDEX, DIFUNCTIONAL COMPOUNDS INTRODUCTION 1 PREPARATION OF ALKYNES
2 PREPARATION OF ACID DERIVATIVES AND 3 4 5 6 7 8
9 10 11 12 13 14 15 16
ANHYDRIDES PREPARATION OF ALCOHOLS PREPARATION OF ALDEHYDES PREPARATION OF ALKYLS, METHYLENES AND ARYLS PREPARATION OF AMIDES PREPARATION OF AMINES PREPARATION OF ESTERS PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS PREPARATION OF HALIDES AND SULFONATES PREPARATION OF HYDRIDES PREPARATION OF KETONES PREPARATION OF NITRILES PREPARATION OF ALKENES PREPARATION OF OXIDES PREPARAflON OF DIFUNCTIONAL COMPOUNDS AUTHOR INDEX
xi xv xvi xvii 1 6 16 54 66 117 139 166 184 200 210 220 242 247 267 276 561
IX
ABBREVIATIONS Ac
Acetyl
acac
Acetylacetonate azo-bis-Isobutyronilrile Aqueous
AIBN
9-Borabicyclo[3.3.1Jnonyl 9-BBN BINAP Bn
9-Borabicyclo[3.3.l]nonyl 2R,3S-2,2'bis-(diphenylphosphino)-111'-binapthyl Benzyl Benzoy 1
BOC
t-Butoxycarbo~~yl
BPY (BiPY) Bu CAM CAN Cat.
2,T-Bipyridyl n-Butyl Carhxamidometliyl Ceric ammonium niuate CycloCatalytic
Cbz
Carbobenzyloxy
Chirald COD COT CP CSA
2S,3R-(+)-4-Dimelhylamino1,2-diplienyl-3-me(hylbutan-2-ol
Bz
C-
CrAB
1,S-Cyclooc~xlienyl 1,3,S-Cyclooctatrieny1 Cyclopentadienyl Camphorsulfonic acid cetyltrimethylammonium bromide
Cy (c-C~H 1 1)
Cyclohexyl
"C DABCO Dba DBE DBN DBU DCC DCE
Temperature in Degrees Centigrade
1,4-Diazahicyclo[2.2.2]octa11e
Dibenzylidene acetone 1,2-Dibrornoethane 1,S-Diazabicyclo[4.3.0]non-S-ene
1,8-Diazabicyclo[S.4.0]undec-7-ene 1,3-DicycloIicxylcarbodiimide I ,2-DichIorcleUiruie
0
)(lotau
0
+OCH2Ph
C@j3NMe3+ Br-
to
BICH2CH2Br c-C@ 1~-N=C=N-C-C&I 1 3 ClCH2CH2CI
xi
xii
ABBREVIATIONS
DDQ % de DEA DEAD Dibal-H Diphos (dppe) Diphos-4 (dppb) DMAP DME
2,3-Dichloro-5,6-dicyano-l,4-benzoquinone % Diastereomeric excess Diethylamine Diethylazodicarboxylate Diisobutylaluminum hydride 1,2-6is-(Diphenylphosphino)ethane 1,4-bis-(Diphenylphosphino)butane 4-Dimethylaminopyridine Dmethoxyethane
DMF
N,N'-Dimethylformamide
DmP DPm DPPb
DDPe DpDf DPPP Dvb e'
%ee I 3
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
HN(CH2CW2 Et02C-N=NC02Et (Me2CHCH2)2AlH Ph2PCH2CH2PPh2 Ph2P(CH2)4PPh2 MeOCH2CHzOMe
bis-[1,3-Di@-rnethoxyphenyl)-1,3-propanedionatoI Dipivaloylmethanato Ph2P(CH2)4PPh2 1.4 -bis-(Diphenylphosphino)butane 1,2-bis-(Diphenylphosphino)ethane Ph2PCH2CHzPPh2 bis-(Dipheny1phosphino)ferrocene 1,3-bis-(DiphenyIpliosphino)propane PhzP(CH213PPh2 Divinylbenzene Electrolysis % Enantiomeric excess 1-Ethoxyethyl EtO(Me)CHOEthyl -CH2CH3 Erhylenediamine H~NCH~CHZNH~ Erhylenediaminetetraacetic acid Flavin mononucleotide tris-(6,6,7,7,8,8,8)-Heptafluoro-2,2-dimethyl-3,5-oc~edio~te Cyclopentadienyl-his-carbonyl iron Flash Vacuum Pyrolysis Hour (hours) Irradiation with light 1,5-Hexadienyl Hexamethylphosphoramide (MeW2P-O Hexamethylphosphoxustriamide tMe3W3P Isopropyl -CH(CH3)2 Lithium cyclohexylisopropylamide Lithium diisopropylamide LiN(iPr)2 Lithium hexamethyldisilazide LiN(SiMe3h Lithium 2,2,6,6-tetramethylpiperidide Methylaluminum bis-(4-bromo-2,6-di-tert-butylphenoxide) bis-(2,6-Di-t-butyl-4-melhy1phenoxy)methylaluminum meta-Chloroperoxybenzoicacid Methyl -CH3 MeOCH2CW2OCHzP-Methoxyetiloxymethyl 2,4,6-tri-Me-C6H2 Mesityl
xiii
ABBREVIATIONS MOM Ms MS MTM NAD NADP Napth NBD NBS NCS NIS Ni(R) Oxone
@
Methoxymethyl Methanesulfony1 Molecular Sieves (3A or 4A) Methylthiomethyl Nicotinamideadenine dinucleotide Sodium triphosphopyridine nucleotide Naphthyl (CioH7) Norbomadiene N-Bromosuccinimide N-Chlorosuccinimide N-Iodosuccinimide Raney nickel 2 KHSOyKHSOq*K2S04
MeOCH2CH3S02MeSCH2-
Polymeric backbone
PCC PDC PEG
Pyridinium chlorochromate Pyridinium dichromate Polyethylene glycol
Ph
Phenyl
PhH PhMe Phth Pic
Benzene Toluene Phthaloyl 2-Pyridinecarbox y late
Pip
Piperidyl
Pr
n-Propyl
PY
Pyridine
quant. Red-Al sBu sBuLi Siamyl TASF TBAF TBDMS TBHP (1-BuOOH) t-Bu TEBA TEMPO TFA
Quantitative yield [(MeoCH2CH20)2AIH21Na sec-Butyl CH3CHaH(CH3) sec-Butyllithium CH3CH2CH(Li)CH3 Diisoam yl [(CH3)2CHGH(CH3)-12 tris-@iethylamino)sulfoniumdifluorotrimethyl silicate Tetrabutylammonium fluoride n-BuqN+ F' t-Butyldimethylsil yl f-B uMe2Si . . f-But&ydroperoxide Me3COOH tert-Butyl -C(CH3)3 Trieth ylbenzylamrnonium Bn(Et)3N+ Tetramethylpi~ridinyloxyfree radical Trifluoroacetic acid CF3COOH
-CH2CHzCH3 N
3
xiv TFAA Tf (OTf) THF THP TMEDA TMS TMP TPAP To1 Tr TRIS Tsvos)
)))I)))) x,
ABBREVIATIONS Trifluomamtic anhydride Triflate Teuahydrofuran Tetrahydwyran Tetramethy lethy lenedidiamine Trimethylsilyl 2,2,6,6-Tetrrunethylpiperidine tetra-n-Propylammoniumperruthenate Tolyl Trityl Triisopropylphenylsulfo~~ yl Tosyl = p-Toluenesulfonyl Sonication C h i d auxiliary
(CF3CO)20 -SOzCF3 (-0S02CF3) Me2NCH2CH2NMe2 -Si(CH3)3 4-CbHqCH3 -CPh3 4-MeC6H4SO2-
::
,DCC
2. AcOH
w
Dussault. PJ Sahli, A. J. Org. Chem., 1992, 57, 1009.
0
0 CoCl2, CH2C12,40°C , 8h
0 OMe
91%
Srivastava, R.R.; Kabalka. G.W, Tetrahedron Lett., 1992, 33, 593. BBr3, A1203 , RT , 2 0 h m
C
O
2
H
Bains, S.; Green, J.; Tan, L.C.;
SECTION 18:
m.R.M. ;&&&a.
0
* 67% G.W. Tetrahedron Lett., 1992, 33. 7475.
ACID DERIVATIVES FROM ALCOHOLS AND THIOLS
Kabalka. G.W,; Chatla, N.; Wadgaonkar, P.P.; Deshpande, S.M. Synth. Commun., 1990, 20, 1617. [(CxH17)3NMe13+{XOO"O)(02)21~)~3 PhCH2OH 4% aq. H202,9OoC
t
Ph-COOH
Venturello. C.; Cramharo, M. .I. Org. Cheni., 1991, 56, 5924.
Singh, M.; Singh, K.N.; Dwivedi, S.; Misri. R.A, S,pthesis, 1991, 291.
85%
Compendium of Organic Synthetic Methods, Volt?
8
+
-
HOOC
NaIO4, RuC13.3 HzO MeCN-CC14-HzO
Y- Y- B
*
DT
Section 19
Singh, A.K.;Varma, R.S. Tetrahedron Lett., 1992, 33, 2307.
SECTION 19: ACID DERIVATIVES FROM ALDEHYDES
Mark6.; Mekhalfia, A. Tetrahedron Lert., 1990, 31, 7237. NaC102, AcOH
E
€
eCHO
*
cnzci2
Etec 84%
w Perez, ; F.; Courtieu, J. Bull. SOC. Chim. Fr., 1990, 127, 565.
oCo2H 86%
0.8% NiCdmp)z, 3 h
Ni(dmp)z = bis-[ 1,3-di@-methoxyphenyl)-1,3-propanedionato nickel 01) Yamada, T.; Rhode, 0.;Takai,T.; M u k a i v w Chem. Lett., 1991, 5. 1. Bu3SnLi 2. Me3SiCN
PhCHO
4
3.3 eq. BuLi 4.03, CHzC12 Linderman.;Chen, K. Tetrahedron Left., 1992. 33, 6767. COCIZ.DCE ,0
PhCHo Bhatia, B.;
2
Ac20.20 h ,25"C
*
Tetrahedron Lett., 1992, 33, 7961.
PhCOOH
PhCOOH
63%
4,%
Section 21
9
Acids from Amides
ACID DERIVATIVES FROM ALKYLS, METHYLENES AND ARYLS
SECTION 20:
OAc
OAc
RuC13 , HIO4, CC4
HO2C
MeCN.If20 25-40°C
Ph
A 76%
NuRez, M.T.; Martin. V.S.J. Org. Chem., 1990, 55, 1928.
ace,,-
Br 1. Tic14 , CH2C12 , RT PhSeA COzEt
*
(Q ..),
2. NaOH , NaE3H4, EtOH RT ’ Inin
70%
. . Sllvelra.; Lenarao, E.J.; Comasseto, J.V.; Babdoub, M.J. Tetrahedron Lett., 1991. 32, 5741.
SECTION 21:
ACID DERIVATIVES FROM AMIDES 1.3 eq.
Me
.
NHn-Bu
~~n/anti=99.5/0.5
Me Me AcO+ C1
Me 0
76% 3 mt3,0.1 DOM ~ P+OH CH2C12, RT, l l h Me 2.4 LiOH RT,30h s~mti=99.uo.8
.
Tsunoda T.; Sasaki, 0.;I d , S. Tetrahedron Lett., 1990, 31, 731.
Ph
)r NH2
0
NzO4, MeCN -20°C
-
d
Ph - C02H
Kim.;Kim, K.; Park,Y.J.Tetrahedron Lett., 1990, 31, 3893.
SECTION 22: ACID DERIVATIVES FROM AMINES NO ADDITIONAL EXAMPLES
86%
Compendium of Organic Synthetic Methods, Vol8
10
Section 23
SECTION 23: ACID DERIVATIVES FROM ESTERS
60% (93% ee) Belair, N.; Deleuze, If.; Rascle, M.-C.; Maillard, B. Tefrahedron Lett., 1990, 31, 653.
D&&QJ!:.
1. A113 ,MeCN
Ph
0
OMe
82"C, 30 min
Mahajan, A.R.; Dutta, D.K.;
0
88% ;
Me
PhA0J)pJ
Ph-CO2H
w
2. H 2 0
Terrahedron Lett., 1990, 31, 3943.
DDQ ,reflux, 8 h
PhC0,H
/
90%
OMe
lb.L%L: Kim. H.R.;Yi,K.Y.Telruhedron Left., 1990, 31, 5913. Ph? Huang,
Br
0
z-z.;
ElOH
* Ph--\
CO2H
81%
- Synrhesis, 1990, 633.
OH
Ph
10% Se ,NaBH4, DMF
&C02Me A \
ih2NEt9MECN-HzO, 30°C I0 khar , 4 d
:
.r
Ph X C 0 , H
A
91%
Yamamoto.: Furuta. T.; MaIsuo, J.; Kurata, T. J. Org. Chem., 1991, 56, 5737.
n-Cl1H23CO2Bn
1. PhMe , MgI2 , reflux , 2 h 2. aq. HCI w
n-C,1H,,CO,H
70% Marlinez. A.G.; Barcina, J.O.; del Veccin, G.H.; HanackM.; S u b r m i m , L.R, Tefrakdron Lett., 1991.32, 5931.
Section 25
11
Acids from Halides
HCOOH ,H 2 0 , reflux
v 0
3h
84%
Schmid, C.R. Tetrahedron Lett.. 1992, 33, 757.
-0
--
- ~--
C0ZH
Troll.$; Wiedemann, J. Tetrahedron Leu., 1992, 33, 3847. Ph
T~BU
CuC12.2 H@ , acetone
PhC02H
96%
PhC02H
92%
RT
0
68%
Dabdoub.;Viana, L.H. Synth. Cornrnun., 1992, 22, 1619. BI3*NEtzPh, PhH , 2 h
PhC02Me
H2O,8ODC
c.
Kabalka.;Narayana, C.; Reddy, N.K. Synth. Comtnun., 1992. 22, 1793. Other reactions useful for the hydrolysis of esters may be found in Section 30A (Protection of Carboxylic Acids).
SECTION 24:
ACID DERIVATIVES FROM ETHERS, EPOXIDES AND THIOETHERS
44%
Fukumasa, M.; Furuhashi, K.; Umezama, J.; Takaha,phi. 0.;Hirai, T. Tetrahedron Lett.. 1991, 32, 1059.
SECTION 25:
PhCH2Cl
ACID DERIVATIVES FROM HALIDES AND SULFONATES em(Ni anode/OH-), t-BuOH/HzO
K2CO3 , 6 0 T Borsotti, G.P.; Foa', M.; Gatti. N, Synthesis, 1990, 207.
c.
PhCOOH
70%
12
Compendium of Organic Synthetic Methods, Vol8
Section 25
Schiinecker.;Walther.; Fischer, R.; Nestler, B.; Bdunlich, G.; Eibisch, H.; Droescher, P. Terrahedron Lett., 1990, 31, 1257.
PhCH2Br
20 eq. NaOCl , MeCN , RT +
PhCHO
2 h )">)
+
PhCOOH
22%
74%
Khurana. J.M,; Sahoo. P.K.; Titus, S.S.; Maikap, G.C. Synrh. Commun., 1990, 20, 1357.
0.5 Ni(CN)2*4 H 2 0 0.5 C0C12.6 H20 , 2 KCN
phk Br
3:1 CO:H2 , PhMe
5N KOH , PEG-400,3.5 d*
Br
phY7Co2H
72%
(1:l cis:trans) Grushin, V.V.;
Terrahedron Lett., 1991, 32, 3349.
\ / I .(It-
-
PdC12(PPh3)2, EtOH CO (30 a m ) , HCl , TlIF
Me0O -
H20,24h,100"C * c1 84% MS 4A . . Terrahedron Lett., 1991, 32, 4733. Urata, H.; Hu, N-X.; Maekawa, H.; 1. Pd(OAc)z(PPh3)2 DMF ,25"C
2. CO , AcOK
*
P h O C 0 , H 82%
Cacchl.;Lupi, A. Terrahedron Lett., 1992. 33, 3939.
Okano.; Harada, N.; JQjjJ,, Bull. Cherrt. SOC.Jpn., 1992, 65, 1741. PdClz(dpm)z, NaOH , CO
Br Okano.,Okabe, N.;
heptane/H~O,50°C
*
%C0,H
Bull. Chem. SOC. Jpn., 1992, 65, 2589.
63%
Acids from Nitriles
Section 28
13
SECTION 26: ACID DERIVATIVES FROM HYDRIDES NO ADDITIONAL EXAMPLES
SECTION 27: ACID DERIVATIVES FROM KETONES hv (Pyrex) , 5 % aq. acetone propylene oxide
Ph
*
Me
Me PhACOzH
58% Sonawane. H.R.; Kulkami, D.G.; Ayyangar, N.R. Tetrahedron Leff.,1990, 31, 7493.
Me W
N a 0 2 . W(HF),
M
e
M e b c o z H 80%
Qlah. G.pL; Ramos, M.T.; Wang, Q.; Surya Pr&&&.&,SynLelt, 1. f-BuOK ,CHCI3 hexane
0 p h y Me
2. H2, Pd-C
1991, 41.
- -r
CO,H
Ph
65%
Llama. E.F,; del C a m p , C.; Sinisterra, J.V. Org. Prep. Proceed. lnt., 1992, 24, 165.
SECTION 28: ACID DERIVATIVES FROM NITRILES
CN Cohen, M.A.; Sawden, J.;
nitrile hydralase SP 361 pH 7 ,30°C , 2 3 h
Tetrahedron Lett., 1990, 31, 1223.
-
Rhodococcus sp , strain CH5 pH 7 buffer, 435 h , RT
C I O C 0 , H
(44% conversion)
Honicke-Schmidt, P.; M
NC-COOH
r
98%
. M.P. .I. Chem. Soc., Chem. Commun., 1990, 648. enzyme fmm Rhddococcus sp.
HOOC-COOH
68%
de Raadt, A; Klempier, N.; Faber, K.; Griencl. H.J. Chem. Soc., Perkin Trans, I, 1992, 137.
14
Compendium of Organic Synthetic Methods, Vo18
OBn -
Rhodococcus bufanica ATCC 21 197
--
CEN CnN
Section 30A
f i
CIN CO2H
68%
(90% ee , S)
Kakeya, H.; Sakai, N.; Sano, A.; Yokoyama, M.; Sugai, T.; Ohm. H, Chein. Leu., 1991, 1823.
SECTION 29: ACID DERIVATIVES FROM ALKENES 1 . HBBrySMe2 ,40°C CH2Cl2.2 h
m C O 2 H
2
2. HzO ,25"C, 30 min 3. CrO3, aq. AcOH 25"C, 12 h Racherla, U.S.; Khanna, V.V.;Brown. H.C, Tetrahedron Left.,1992, 33, 1037.
SECTION 30:
97%
ACID DERIVATIVES FROM MISCELLANEOUS COMPOUNDS 1. cuc12 2. H20
PhN2' BF; * PhCOOH Olah.;Wu, A.; Bagno, A,; Surya Prakash, G.K.S.SynLett, 1990, 596. SECTION 30A:
Ph\
PROTECTION OF CARBOXYLIC ACID DERIVATIVES 1. MgBq ,ether 2. H20
COZMOM
b
Ph\
Kim.; Park,Y.H.; Kee, I.S. Tetrahedron Lett., 1991, 32, 3099.
EtCooH
42%
'*
Ph
phhoH (86-95%) OH Ph
2. LDA , TMSCl
(82-g4%)
NaOH , aq. MeOH ,reflux, 2 h Waldmiiller, D.; Braun. M,; Steigel, A. SynLett. 1991, 160.
C02H
Section 30A
OBn BnO&COzEn
15
Protection of Acids
EtOH , 10%Pd-C ,23"C
Tetrahedron Lett.. 1992, 33, 2299.
OBn BnO&C02H
90%
Other reactions useful for the protection of carboxylic acids are included in Section 107 (Esters from Carboxylic Acids and Acid Halides) and Section 23 (Carbxylic Acids from Esters).
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 3 PREPARATION OF ALCOHOLS
SECTION 31: ALCOHOLS AND THIOLS FROM ALKYNES NO ADDlTIONAL EXAMPLES
SECTION 32:
ALCOHOLS AND THIOLS FROM ACID DERIVATIVES Et3N*BH3 , 8 0 ° C , 4 h
-C02H
O -H
96%
Kfii, 0.;PlzAk, 2.; PleSek, J. Coll. Czech. Chem. Commun., 1990, 55, 2956.
co2H
1. N-methyhofpholine N-oxide
CIC02EtI THF , -10°C 2. NaBH4, MeOH , 2 0 min
CbzHNT Ph
Ph
Synthesis, 1990, 299. BnEt3N' BH4- , Me3SiCI
PhCOOH Das, J.;
CH2Clz
*
'hCH2OH
92%
b a r d Synrh. Commun.. 1990, 20,901.
PhC0,Me
1. [5% CpzTiC12/10% BuLi] ,RT THF , -78"C,2 eq. HSi(OEt)3
PhCH2OH
2. conc. HCI Berk, S.C.; Kreutzer, K.A.; Buchwald.S.L.. Am. Chem. SOC.,1991, 113, 5093.
Ph-7
NaBH4, 1 2 , RT 1nF
CO2H PhxOH Kanth, J.V.B.; Periasamv. M,.I, Org. Chem., 1991, 56, 5964.
98%
93%
Section 32
Alcohols from Acids
17
2 eq. SmI2, THF/H20 NaOH , RT
* @OH
58 sec
78%
Kamochi, Y.; Kudo. T, Chem. Lett., 1991, 893. N a B Q ,catechol
n-C8H&H,OH
F A ,4 h
n-C8H17C00H
87%
Suseela, Y .;
Tetruhedron, 1992, 48, 371.
SmI2-85%H3P04
Ph-CO,H
--
THF , 3 sec
PhCH2OH
91%
Kamochi. Y Kudo, T. Tetrahedron, 1992, 48,4301, t;
.
1. h v , 0 2 . 2 h acridine PhMe r
-
B
u
h
c
o
2
H
2. Me2S , MeOH*
t
-
B
u
h
Fe (porphyrin) , RT PhIO , CH2Cl2 ,20 h
-
'">OH
H
6070
Okada.;Okubo, K.; QhJL Tetrahedron Lett., 1992, 33, 83.
Ph
O
+
'$0
3% 46% Komuro, M.; Nagatsu, Y.;Higuchi, T.; Hirobe. M. Tetrahedron Lett., 1992, 33, 4949.
fli~
NaBH4-HzS04
89%
Abiko. A,; Masamune, S. Tetrahedron Lett., 1992, 33, 5517. 1. e- ,NaBH4
n-C7H ISCOOH Shundo, R.; Matsubara.;-;
PhCOOH -hi.
2. HzO
-
n-C7H15CH20H
70%
Hirashima, T. Bull. Chem. SOC. Jpn., 1992, 65, 530. 4 eq. SmI2,8 eq. NaOH 1-120 *
PhCH2OH
Y.; Kudo, T. Bull. Chem. SOC. Jpn., 1992, 65,3049.
92%
18
Section 34A
Compendium of Organic Synthetic Methods, Vol8
Zn(BH& , DMF , 2 4 h
n-C7H,,COOH
TFA
n-C7H15CH20H
@
90%
Ranu. B.C. ; Das, A.R. J. Chem. SOC., Perkin Trans. I, 1992, 1561.
SECTION 33:
ALCOHOLS AND THIOLS FROM ALCOHOLS AND THIOLS
OSiMe,
BuLi , THF , -78°C
TiMe3
*
A SnBu,
n-C7H15
OH 63%
n-C7H15
reverse Brook rearrangement Linderman. R.J. ; Ghannam, A. J. Am. Chem. SOC., 1990, 112, 2392. 0
FAN)
"MeYSH THF , PP ,
H?. H
PhaMe
0
2
*
2. LiAIH4, ether
Ph
>SH Me
61%
(96% ee)
Corev. EL; Cimprich, K.A. Tetrahedron Lett., 1992, 33, 4099.
SECTION 34: ALCOHOLS AND THIOLS FROM ALDEHYDES The following reaction types are included in this section: A. Reductions of Aldehydes to Alcohols B. Alkylation of Aldehydes, forming Alcohols. Coupling of Aldehydes to form Diols is found in Section 323 (Alcohol-Alcohol).
SECTION 34A:
G
REDUCTIONS OF ALDEHYDES TO ALCOHOLS
z
h
Zn(BH4)2, THF , -10°C
0 selective reduction of aldehydes in the presence of ketones
Ranu.; Chakraborty, R. Tetrahedron Lett., 1990, 31, 7663.
0
quant.
Section 34B
Alcohols from Aldehydes
-CHO
DMF- 1 3 2 0
19
-OH
-
98 %
also with aromatic and conjugated aldehydes
Wmg, W-B.; UL- Tetrahedron L.; Lett., 1990, 31, 1185. Zn-ZnClz 50% aq. THF
Tanaka, K.; Kishigami, S.;
+ 7%
81% of dimeric diol
Toda.F.. Org. Chem., 1990, 55, 2981.
0
hv ,cyclooctane , 4 8 h
RhCI(CO)(PMe3)2
CHO
P
Sakakura, T.; Abe, F.;
O
H
87%
Chem. Lett., 1990, 583, 585. XP4 - Zn(BH&, EtOH
PhCHO
reflux, 8 h
t
PhCH20H
80%
XP4 = crosslinked poly(4-vinylpyridine)
Flrouzabadi..H.; Tamami, B.; Goudarzian, N. Synth. Cornmun., 1991, 21, 2275. PhCHO
NiC12-6 H 2 0 , aq. DMF 30 min
c
PhCH2OH
95%
PhCH20H
98%
IbmaLR& Tetrahedron Lett., 1992, 33, 5417. PhCHO
NaBlI4 , PhH , H 2 0 , RT H-montmorillonite , 7 h
*
Subba Rao, Y.V.; (3houdarv. B.M.Synth. Commun., 1992, 22, 2711.
SECTION 34B: ALKYLATION OF ALDEHYDES, FORMING ALCOHOL ASYMMETRIC ALKYLATIONS 1.
>CHO
ether, - 1 ~ O c .30 min
2. NaOH ,H 2 0 2
*
Racherla, U S . ; Brown.H.COrg. .. Chem., 2991, 56, 401.
(96% ee)
Compendium of Organic Synthetic Methods, Vol8
20
Section 34B
Corev.:Kim, S . S . Tetrahedron Lett., 1990, 31, 3715.
M = ally1 ZnLiCl , THF , 0°C M = AIMe3Li. ether, -78OC
98
2 84
16
Overly, K.R.; Williams, J.M.; UQLYQ&L Tetrahedron Lett., 1990, 31, 4573.
(70%) (78%)
(70% dr)
Henedus.; Imwinkelried, R.; Alarid-Sargent, M. J. Am. Chem. Soc., 2990, 112, 1109.
=c
PhCHO
SiMe3
OiPr
*
20% BH3.THF/ O
OiPr
Furata, K.; Mouri, M.;
OBn CHO
>
Nehry, K.J. Jr.;
r
OH
SynLert, 1991, 561.
-
(82%ee , R)
OBn
J SnMe3 ,ether
5M LiC104, 1.7 h
phxx
m
OH
(291 dr) ; Jape, C.T. Tetrahedron Lett., 2992, 33, 1817.
82%
82%
Section 34B
Alcohols from Aldehydes
PhCHO , CH2Cl2 -780c
+OSiMe,t-Bu
OEt
OH OSiMe2t-Bu
t
Ph
+o
21
JdOEt -
77%
(45% ee)
Ts'"B H
Kivooka. S.; Kaneko, Y.; Komura, M.; Matsuo, H.; Nakano, M. J. Org. Chem., 1991, 56, 2276.
5)
(1
Li
=/ ,ether ,RT (6 &~w.LB&; Carpenter, A.J. Tetrahedron Lett., 1992, 33, 1697.
1)
Reactions of EtZZn and PhCHO Et& , hexane , RT , 2 d
PhCHO A1203
Me +Ph
Fj
Me
0
PhyEt OH
(43% ee , R)
81%
Soai.;Watanabe, M.; Yamamoto, A. J. Org. Chem., 1990, 55,4832. EgZn , PhMe ,20 h
PhCHO
w
"EPh
6%
OH
HO
Rosini, C.; Franzini, L.; Pini, 0.;
CHO
Et"' H
99%
(ym
Tetrahedron Asyrnmeiry, 1990, 1 , 587.
,,,.qH
I
Y OH
(77% ee , R)
.
EtzZn, RT , 4 8 h
Me-
Ph
H
Me
* (1:l (251
40%
73%
90% Chaloner, P.A.; Langadianou, E. Tetrahedron Lett., 1990, 31, 5185. (4.51
O%ee
)
80%ee )
97.5% ee)
22
Compendium of Organic Synthetic Methods, Vol8
Ph>CHO Me
-
Et2Zn HOCH2CHzNH2
Section 34B
OH
P h y C + (83% dr, syn) Me
phy% 55% Me
Soai.;Niwa, S.; Hatanaka, T. Bull. Chem. Soc. Jpn., 1990, 63, 2129. EtzZn , hexane , -10°C ,24 h
<ELOH
CHO
67%
(95% ee ,R)
Hayashi, M.; Kaneko, T.; Qguni. N, J. Chem. SOC.,Perkin Trans. 1, 1991, 25.
PhCHO
EtzZn, 5%ephedrine
*
OH PhlEt
(66%ee , R)
60%
Chaloner. P.A,; Langadianou, E.: Peresa, S.A.R. .I. Chent. Soc., Perkin Trans. I, 1991, 2731.
Ph
Et2Zn
PhCHO
7 8 '
OH
I 3
92%
(96% ee)
3
Asami.;Inoue, S. Chem. Lett., 1991, 685.
Et2Zn , PhMe ,20 h
PhCHO
6%
*
94%
(63%ee ,S)
NMe2 NMe2
\
OH x Et H
Ph
\
(S) Rosini, C.; Franzini, L.; Iuliano, A.; Pini, D.; Salvadori. P, Tetrahedron Asymmetry, 1991, 2 , 363. EtzZn, PhMe ,20 h
PhCHO
t
OH ph99:1 E:Z ;
a : y substitution)
Yanagisawa, A.; Habaue, S.; Yamamoto. H. J. Am. Chem. Soc., 1991, 213, 8955. 1. CsF , MeCN 2. ECHO
Ph
-IMe %Me3
SMe
*
Ph%Et OH
Ph--/
+
SMe
27%
26% Bonini, B.F.; Masiero, S.; Mazzanti, G.; Zani. P, Tetrahedron Lett., 1991, 32, 815.
Br
Me0,C- C: C 7 1. BuLi , -78°C
0
,OH
-
2.TiCl(OiPr)3 3. -60°C. 21 h Me02C- C3 C
3CHO
70%
0
Haannann, H.; Eberbach, W.Tetrahedron Lett., 1991, 32,903.
ClF,C
iPrCHO , Zn-CuC1
SiMe, DMA ,100"C *
& ' r
DMA = N,N-dimethylacetamide
; -
OH
SiMe,
75% Miwatashi, S.; Kuroboshi, M.; Utimoto, K. Tetrahedron Lett., 1991, 32, 1069.
26
Compendium of Organic Synthetic Methods, Vo18
"9
'
OCll F
e
oc
1.
Section 34B
d
.elher
BF-j*OEt2 2. NaI ,wet acetone
55%
Agoston, G.E.; Cabal, M.P.; Turos. E, Tetrahedron Lett., 1991, 32, 3001.
"masked"Li bis-homoenolates Ram6n, D.J.; Y u s . J . Org. Chem., 1991, 56, 3825. 1. CpzZrMe~ 2 . 5 eq. t-BuOK , THF
3. aq. KF
eg /
0
69%
Larson, A.L.; Baker, D.L.; Towne, R.W.; & a u ~ L & Tetrahedron Lett., Z991, 32, 5893.
CHO
<SiMe3
BnOTMS , C C 4 cat. Me3SiOTf Mekhalfia, A.; Mark4 I.E. Tetrahedron Leit., 1991, 32, 4119,
B(OPh), Hara, S.; SJJ&L-&.
PhCHO
0°C -) RT
Tetrahedron Leit., 1991, 32, 6749.
,3h
-Br
In, H 2 0
t
Li, C.J.; €haJX. Tetrahedron Leit., 1991, 32, 7017. Zn , AcOH
-CHO
PhMe , H 2 0
c&
--
Br
PhCHO , THF ,overnight
OH
OH
Ph
91%
7 OH c1
Qda. Y,; Matsuo, S.; Saito, K. Tetrahedron Lett., 1992, 33, 91.
99%
Section 34B
Alcohols from Aldehydes
27
1. Me3SiCi ,Nal , H 2 0 Sn
OH
2. butanal, MeCN RT.4h (98
(35:65 E:Z) J. Org. Chem., 1992, 57, 6988.
Kanagawa, Y.; Nishiyama, Y.;
t
CHO
2)
-b
76%
SiO2 (oven-dried) 15 k b a , CH2C12 25"C, 48 h
OH
58%
2%
Dauben.:Hendricks, R.T. Tetrahedron Lett., 1992, 33,603.
T
C
H
O
'%:
Bu3SnH , PhH ,8OoC
AIBN
Ph
75%
( 2 5 2 5 3 . 0 :1.0)
Enholm. E.J; Burroff, J.A. Tetrahedron Lett., 1992, 33, 1835. 1. PhCHO , THF , -78°C Li powder/CloHNb , 2h
ClJCCl
Ph m
2. H20
p
h 73%
Ram6n, D.J.; h s . M Tetrahedron Lett., 1992, 33, 2211. PhCHO , Cd , THF
+Br
b
Bu4NBr, 4 h OH Sain, B.; Prajapti, D.; Sandhu. J.S. Tetrahedron Lett., 1992, 33, 4795.
90%
1. b S n B u 3 .RT
PhCHO Marshall, R.L.;
2.F'
MeSiC13 , CH2C12, 6 d
+
Ph
Tetrahedron Lett., 1992, 33, 1365.
quant
28
Compendium of Organic Synthetic Methods, Vo18
,THF,RT
&Br
-CHO
cat. CpzTiClz , Zn , RT
Dine.;Zhao, G. Tetrahedron LRtt.,
* 3 min 1992. 33, 81 17.
Section 34B
A
80%
61% Davis. A.P, ; Jaspars, M. Angew. Chem. Int. Ed. Engl., 1992, 31, 420. PhCHO , SnC12, DMF
2% PdClZ(PhCN)z, 25°C
-OH
4
63 h
Takahara, J.P.;
P
63%
h
(3070 dr)
-Y.;
Kurusu, Y . J. Am. Chem. SOC., 1992, 114, 2577.
MeCrCIz(THF)3, THF
PhCHO
-60°C + 20”C,18 h
b
ph-(Me
OH
90%
ann. T.; Beirich, C.; Hamsen, A.; Moller, T.; Philipp, C.; Wingbermuhle, D. Chem. Ber., 1992, 125, 157. REVIEWS:
“Addition of Organochromium Compounds to Aldehydes: the Nozaki-Hiyama Reaction” Qntas. P , Synthesis, 1992, 248.
SECTION 35:
ALCOHOLS AND THIOLS FROM ALKYLS, METHYLENES AND ARYLS
No examples of the reaction RR1 + ROH (R1 = alkyl, aryl, etc.) occur in the literature. For reactions of the type RH -+ ROH (R = alkyl or aryl) see Section 41 (Alcohols and Phenols from Hydrides). 1. Brz , CHZC12 2. HF*Py , 0°C
AcO
3.30% HzOz , KF * KHC03, THF AcO’” AcO”‘ MeOH Magar, S.S.; lWu2.L. Tetrahedron Lett., 1991, 32, 7513.
Section 38
Alcohols from Esters
29
SECTION 36: ALCOHOLS AND THIOLS FROM AMIDES SmI2, LiNH2, THF MeOH , RT , 3 secn-
Ph y NH2
ph-
0 Kamochi, Y.;
OH
72%
Tetrahedron Lett., 1991, 32, 351 1.
SECTION 37: ALCOHOLS AND THIOLS FROM AMINES NO ADDITIONAL EXAMPLES
SECTION 38: ALCOHOLS AND THIOLS FROM ESTERS HSiMe3 ,CO , PhH cat. C02(CO)8 ,25"C 1 am.
M e o w O A c
M e O ~ o s i M e 3
76% Chatani, N.; Sano, T.; Ohe, K.; Kawasaki, Y.;Murai. S. J. Org. Chem., 1990, 5.5, 5923. SmI2, LiNH2, THF MeOH , RT , I 4 min
Ph y OMe
ph7
0
OH
64%
Kamochi, Y . ; Kudo. ZTetrahedron Lett., 1991, 32, 3511.
-
Aco-0-
Pseudomoms cepacia lipase P-30
oAc
4h
H O O O A c
64%
(79% ee) Harris, K.J.; Gu, Q.M.; Shih, Y-E.; Girdaukas, G.; Sih. C.J, Tetrahedron Lett., 1991, 32, 3941. 1. Bu3Sn20, PhMe 80°C , 2 h
OAC
-2.'
2. pH 4
h
Salomon, C.J.; Mata, E.G.; Mascaretb.. O.A, Tetrahedron Lett., 1991, 32, 4239.
96%
NaBH4,ZnCIz. 2 h
Ph
Co2Et
PhNMe2, THF * 85% reflux Yamakawa. T,; Masaki, M.; Nohira, H. Bull. Chem. SOC. Jpn., 1991, 64, 2730.
30
Compendium of Organic Synthetic Methods, Vo18
Section 39
n-C5Hl lCHO , DMF ,4O"C NiC12(PPh3)-Zn , 7 h
WJ.; Konishi, H.; Matsuura, H. Chem Lett., 1991, 2023.
P h 7
5% Ti(OiPr)4,5S0C 3 eq. SiH(OEt)3 , 4 h
CO2Et
Ph7.0H
89%
Berk, S.C.; Buchww. S.L.J. Org. Chem., 1992, 57, 3751.
ALCOHOLS AND THIOLS FROM ETHERS, EPOXIDES AND THIOETHERS
SECTION 39:
-
Me
DMF ,60"C
O&
0
+ o
0
+
N3
MeTo 0 +OH
OH
N3
n-Bu3SnN3.5h 15 1 (69%) n-Bu3Sn(N3)2 , 4 h >99 1 (79%) Saito. S; Nishikawa, T.; Yokoyama, Y.;Moriwake. T, Tetrahedron Lett., 1990, 31, 221. I-Bu
I-BU
CH2C12 , -20°C , 3 h
Me
2.O"C , 12h 3. R T , l h
Maruoka, K.; Sato, J.; Banno, H.;
Me 9) 1 Tetrahedron Lelt., 1990, 31, 377.
92%
MeLi , THF , -78°C Me
OBn Arjona, 0.; 1475.
87% ; Mallo, A.; Plumet, J.; Viso, A. Tetrahedron Lett., 1990, 31,
Section 39
Alcohols from Ethers
31
BIs*PhNEt.r, PhH
Ph-OMe
*
3h
Ph-OH
85% Narayana, C.; Padmanabhan, S.; Kabalka, G.W. Tetrahedron Lett., 1990, 31,6977.
Y,Tetrahedron Lett., 1990, 31, 7467. secBuLi-CuCN
OTBDMS THF , 0°C + RT OTBDMS
90%
4)
(96
Sugita, K.; Onaka. M,; Izumi.
secBu
OTBDMS OTBDMS
73% no reaction with MeLiKuCN or n-BuLilCuCN; 78% with t-BuLi/CuCN Lautens.;Smith, A.C.; AM-El-Aziz, AS.; Huboux, A.H. Tetrahedron Lett., 1990, 31, 3253.
Me
1 eq. LDA , THF
-78°C
CS-H
I /
82%
77%
with 3 eq. LDA
Yadav. J.S,; Deshpande, P.K.; Sharma, G.V.M. Tetrahedron Lett., 1990, 31,4495. 1. LDBB , THF
0
-78OC, 2 min
n-C8H17e
. MeOH ,- 7 8 ° C
H
n-C8HI7 * + HO
LDBB = lithium 4,4'-di-t-butylbiphenylide
Cohen.;Jeong, I-H.; 1528.
Ph
n-C8H17
65%
F
H
35%
Mudryk, B.; Bhupathy, M.; Awad, M.M.A. J. Org. Chem., 1990, 55,
0~~ 1. Li , THE 2OoC * 0~~ 2. H20
4
Me
Ph-(oW70%
Azzena.;Denurra, T.; Melloni, G.; Piroddi, A.M. J. Org. Chem., 1990, 55, 5532.
32
Compendium of Organic Synthetic Methods, Vo18
S
Section 39
Bu3SnH , AIBN PhH , reflux
*
a M e 6 8 %
OH
(2.7: 1 )
Rawal. \LfL; Newton, R.C.; Krishnamurthy, V. J. Org. Chem., 1990, 55, 5181. 1. MeMgCl 2. MeMgI ,CuBr
T s A 0
3. aq. NHdCI
56%
Me
Ngiera.;Sansano, J.M. Tetrahedron, 1990, 46, 3993.
MsO
1 . BuEu(CN)Li2 ,THF -20°C
bo
2. BuzCu(CN)Li2. T H F -20°C
BuG
B OH
u
-k
&Bu Bu 1)
(1.2
Kurth. M L; Abreo, M.A. Tetrahedron, 1990, 46, 5085. MeMgI , CuBr , PBu3 O°C
*
75%
0"" 73%
Mitani. M.; Matsumoto, H.; Gouda, N.; Koyama, K. J. Am. Chem. Soc., 1990, 112, 1286.
n-
LxL OOH 78%
2. H3O'
-Bull
(90% ee , S)
Chem. SOC.Jpn., 1990, 63, 721. CpZTiC1, C6Hs
*
ZH
91%
gent, W.A.; Beattie, M.S. J. Am. Chem. SOC., 1990, 112, 6408.
Section 39
Alcohols from Ethers
Zn(BH&/Si02, THF
33
-
Ph-O RT,24h P h M O H 90% Ranu.';Das, A.R. J. Chem. SOC.,Chem. Commun., 2990, 1334. /
KFdumina, ethylene glycol 215OC. 5 h
=OH
80%
Radhakrishna, AS.; Prasad Rao, K.R.K.; Suri, S.K.; Sivaprakash, K.; Sineh, B.B,Synih. Commun., 1991, 21, 379. NaBH4, H 2 0 , RT , 4 8 h P-cyclodextrin
P h d o
*
Phr' -k OH
P h e O H
66% 17% 15% ee , S) (25% ee , S ) Hu, Y.; Uno, M.; Harada, A.; Takahashi. S, Bull. Chem. SOC. Jpn., 1991, 64, 1884.
Bu3SnH , AIBN , PhH (0.05
M)
* Me$ph
syringe pump addition
Ph
Kim.;Lee, S.; Koh, J.S. J. Am. Chem. SOC.,1991, 113, 5106.
Ph-OBn
3 AICl3 , 4 PhNMe2 CH2C12, RT 30 min
82%
H
Ph-OH
93% Akiyama. T.; Hirofuji, H.; Ozaki. S , Tetrahedron Lett., 1991, 32, 1321. Ph3SnH, hv ,70°C .-
Krosley, K.W.;
.*\
Ph-
OH
; Clapp, G.E. J. Org. Chem., 1992, 57, 840.
Dibal , CHzClz -15OC + RT
0 OTs
Chone. J.M.Tetrahedron k i t . , 1992, 33, 33.
P
h (>%
y OH
+
Ph OH Mg anode, Ni foam cathode
t - B u e O4
63%
Espanet, B.; Duilach.; Phichon, J. Tetrahedron Lett.. 1992, 33, 2485.
-
hv ,MeCN-H20, Wt3
NaB H4
OH
Ph-
95%
EDline.;Wang, Q. J. Chem. Soc., Chem. Cummun., 1992, 1133. Me.,G (?H
BuLi ,ether, O°C
*
OH
Me
Lautens.;Belter, R.K. Tetrahedron Lett., 1992, 33, 2617.
Bu
HO BrQ
BuLi
93%
OSiMe2t-Bu Woo, S.;
92%
OSi Me2t-Bu
Tetrahedron Lett., 1992, 33, 2661.
OSiMe2t-Bu
Bu3SnHI AIBN
t-BuMe2Si0 &ph
c
Ph
PhH ,reflux, 3 h
OH
Kim.;Koh, J.S. Tetrahedron Lett., 1992, 33, 7391. S i 0 2 - Zn(BH& ,THF c
m"" (yo. +
(98
Ranu. B.C,; Das. A.R. J. Chem. SOC.,Perkin Trans. I, 1992, 1881.
P0
68%
MeCN , LiBr , RT
t
2)
95%
TBr
OH Amberlyst-15 resin (>99:1) Bonini. C. ; Giuliano, C.; Righi, G.; Rossi, L. Synth. Commun., 1992, 22, 1863.
Section 40
35
Alcohols from Halides
REVIEWS:
T&QLS&
"Biosynthetic, Biomimetic, and Related Epoxide Cyclizations" Org. Prep. Proceed. lnt., 1992, 24, 247.
Additional examples ofether cleavages may be found in Section 4% (Protection
of Alcohols and Thiols).
-
SECTION 40:
ALCOHOLS AND THIOLS FROM HALIDES AND SULFONATES
Br
1. (Bu$n)2O, 20°C 20 h
2. TBAF.3 H2O
-SH 71%
Gingras, M.; mp.D.N, Tetrahedron Lett., 1990, 31, 1397. 1. 1-BuLi,penmelether
-1
-78°C. 5 min 2. pentanal
*
v OH
91%
general method - preparation of 1" organolithium reagents Bailev. W.F,; Punzalan, E.R. .I. Org. Chem., 1990, 55, 5404. 1. t-BuLi , penme-ether -78°C
Bailey. W.F,; Khanolkar, A.D. J. Org. Chern., 1990, 55, 6058. 1. CICH20CH2CH2CI , ether , RT
*
BuMgCl
2. Na-K Q&-!!A; Wilson, T.E.; Stowe, J.A. Synthesis, 1990, 495.
Ph 7 Br
1. TBS-SLi ,ether 0°C - 25°C. 48 h
2. IIF, MeCN
Kraus.:Andersh, B. Tetrahedron Lett., 1991, 32, 2189.
BuCH20H
Ph 7 SH 98%
Olah.;Keumi, T.; Lecoq, J.C.; Fung. A.P.; Olah, J.A. J. Org. Chem., 1991, 56, 6148. 0 2 , CH2C12.3O"C
H hfacac-Zn
M
[( Fe(HBpz3)(hfacac))Ol
21 turnovers Hhfacac = hexafluoroacetyl acetone HBpz3 = hydrouis-1-pyrazolylborate Ito, M.; Fukui, H.; J. Chem. Soc., Chem. Commun., 1991, 102.
. .. m;
P. putida 02
66%
OH
34%
0
(45% ee) Sharma, N.D.; Stevenson, P.J.; Chima, J.; Gray, D.J.; LMuuJL Tetrahedron Lett., 1991, 32, 3887.
Bovd.;
6
0
N
NO, \
I MeCN , 75°C 2. H30+
80%
TMAO = Me3N-0
Reinaud.;Capdevielle, P.; Maumy, M. J. Chem. Soc., Perkin Trans. I, 1991, 2129. Ru(TPP)(CO) , HBr
= ($
%$,PhH,RT,6h
O!H
C1
Ohtake, H.; Highuchi, T.; Hirobe. & J. Am. Chem. Sac., 1992, 114, 10660.
94%
39
Alcohols from Ketones
Section 42A
SECTION 42: ALCOHOLS AND THIOLS FROM KETONES The following reaction types are included in this section: B. Alkylations of Ketones, forming Alcohols A. Reductions of Ketones to Alcohols Coupling of ketones to give diols is found in Section 323 (Alcohol
n-CSH1,
+ Alcohol).
1. M2(OAc)4
CHzClz, RT
2. Nai3H4, C e C l r
b 2
n-C3H7
n-C3H7
(70
30)
86%
Taber.;Hennessy, M.J.; Louey, J.P. J. Org. Chem., 1992, 57, 436. 1 . [Na2COyI .5 H2021 aq. THF *
))))I))
2. AcOH
-
H O G O H 86%
Kabaka. G.W.; Reddy, N.K.; Narayama, C. Tetrahedron Lett.. 1992,33,865.
SECTION 42A: REDUCTION OF KETONES TO ALCOHOLS ASYMMETRIC REDUCTION Bakers yeast
*
CICH2C02Et
OH A C 0 2 M e 51% (91%ee)
Nakamura.; Kawai, Y.; Ohno, A. Tetrahedron Lett., 1990, 31, 267.
SiMe,
(-)IPCzBCI
.
*
3h -35°C 2. HN(CHZCH~&
1.
H
OH SiMe3
67%
( 9 5 % ee)
SoderauistJ.A.;Anderson, C.L.;Miranda, E.I.; Rivera, I.; Kabalka, G.W. Tetrahedron Leff., 1990, 31, 4677.
bakers yeast t
Me
methyl vinyl ketone
OH &CO,Et Me (96
+
OH
i \ ( Co2Et Me 4)
Nakamura.; Kawai, Y.; Miyai, T.; Ohno, A. Tetrahedron Lett., 1990, 31, 3631.
96%
40
Compendium of Organic Synthetic Methods, Vol8
t
Ph
Section 42A
PhA Me
0.1
(87% ee ,R) Rama Rao. A.V,; Gujar, M.K.; Sharma, P.A.; Kaiwar, V. TefrahedronLett., 1990, 31,2341.
C7H8,-78"C, 15h
+
ph&
* Ph >9S%
u; Bakshi, R.K. Tetrahedron Lett., 1990, 31, 611. Ph
n
B ~ H ~
q : Ph
0
\
0.M.P.; Pemer. R.J.; Lijewski,
9 2 % R~ ~
Bu
n
*
Ph
OH
94% ee
Ph
L. Tetrahedron Lett., 1990, 31, 7415.
7 0
Thertrwanaerohiurrihrockii alcohol dehydrogen,zfe
*
7 OH 79% ee , S
Pseudonwnas alcohol dehydrogenase
-b 97%ee,R Shen, G-J.; Wang, Y-F.; Bradshaw, C.; Wong. C-H,J. Cherrr. Soc., Chem Cornmutt., 1990,
677.
BF3*OEt2, PhH , 0°C 3
N4 : ; .
BH3
.L
OH 81% (41% ee, R)
\
Kanth, J.V.B.; Periasamv. M. .I. Chea. Soc., Chewz. Corrzrnun., 2990, 1145.
Section 42A
Alcohols from Ketones
41
kCozH bakers yeast 28h
OH
OH
""'C02H
*
-t
T C O 2 H 30)
(70
67%
(98%ee) (>99% ee) Fuiisawa.;Mobele, B.I.; Shimizu, M. Tetrahedron Lett., 1991, 32, 7055. Zn(cra)*, THF , RT
*
Ph
P 3h
88%
-
(84% ee)
Zn(cra) = zinclsodium chiraldate
Lalloz, L.; Vanderesse, R.; Mayesky, B.; C a u h g L Chern. Lett., 1991, 1961.
Ph
L
7
Rawson, D.;
Ph
Me
L i A M 1 e$0 OMeOM@Me e o m O M . ]
OH I
Ph
THF , -78°C
84%
(94% ee) J. Chem. SOC., Chem. Commun., 1992, 494. Bu3SnH , TBAF , 0°C
*
0
OMe PhylMe OH
OMe Me
+ phLA -OH
0 ) 81% with BuZSnClH , 0°C (10 90) 72% Shibata. I,; Yoshida, T.; Kawakami, T.; Baba, A.; Matsuda, H. J. Org. Chern., 1992, 574049. (100
Bu
99.8% SN2'
B U-Bu
85% Barton, D.H.R.; Jaszberenyi, J.Cs.; LeBmann, K.; Tim& T. Tetrahedron, 1992, 48, 8881.
Section 70
Alkyls from Halides
77
48%
Beueelmans.;Chastanet, J. Tetrahedron Lett., 1991, 32, 3487.
1. M e 0
0
C
0
71% 3.10 eq. Cu powder DMF , reflux Takahashi, M.; Kuroda, T.; Orgiku, T.; Ohmi7.11,H.; Kondo, K.;bm&,L . Tetrahedron Lett., 1991, 32, 6919.
SnBu3, DMF
Me0
Me0 F
OMe PdC12(PPh3)2 , LiCl PPh3, 120°C
OTf
O
M -
e 84%
Saii. J.M.; Martorell, G.; Garcia-Raw, A. J. Org. Chem., 1992, 57, 678. Martorell, G.; Garcia-Raso, A.; SaB, J.M. Tetrahedron Leu., 1990, 31, 2357.
6 I
Br
pQMe
1. Pd(PPh3)4 , DME 2. aq. Na2C03 ,reflux 24 h M
e
Ph
0 B(OH);!
77% 3. Ph-B(OH)z, reflux Unrau, C.M.; Campbell, M.G.; m s . V. Tetrahedron Lett., 1992, 33, 2773.
1 . BuLi 2. LiCloH8, -78°C
0 Phy
Lc1
N'
3. PhI ,-78°C + RT
0 e
lcPh
P&NH
Barluenea.;Montserrat, J.M.; Flbrez, J. Tetrahedron Lett., 1992, 33, 6183.
75%
Compendium of Organic Synthetic Methods, Vol8
78
o\ N
1. Zn* ,THF, RT
2. PhI , Pd(PPh3)d ,THF
Br
Sakamoto, T.; Kondo, Y.; Murata, N.;
HO-Si-
' \
Section 70
*
N
76%
Tetrahedron Lett., 1992, 33, 5373.
I. BuLi 2. BnBr , HMPA
Ph
Ph
D.
Ph-Ph
63%
Hudrlik.;Abdallah, Y.M.; Hudrlik, A.M. Tetrahedron Len, 1992, 33, 6747, 6743.
4
1. t-BuLi ,pentane-ether , -78°C 2. TMEDA 4. MeOH
89%
W.F.; Khanolkar, A.D.; Gavaskar, K.V. J. Am. Chem. Soc., 1992, 114, 8053. Bailev. W.F.; Khanolkar, A.D. Tetrahedron Lett., 1990, 31, 5993. 2e
. 10% PdC12(PPh3)2 t
PhOTf
Ph-Ph 76% DMF , 9 0 T lutand.;NCgri, S.; Mosleh, A. J. Chem. SOC., Chem. Commun., 1992, 1729. 2
-1
B- n-CaH17
vK3p04 Pd(PPhd4
Ishiyama, T.; Abe, S.; Miyaura, N.;
n-C 1qH 30
64%
Chem. Lett., 1992, 691.
-+B(OHh
OMe
2% Pd(PPh3)4, DME-HzO Ba(OH)2 ,8O"C Watanabe, T.; Miyaura, N.;
SECTION 71:
t
'
80%
SynLett, 1992, 207.
ALKYLS, METHYLENES AND ARYLS FROM HY DRIDES
This section lists examples of the reaction of RH + RR' (R.R = alkyl or aryl). For the reaction C=CH + C=C-R (R = alkyl or aryl), see Section 209 (Alkenes from Alkenes). For alkylations of ketones and esters, see Section 177 (Ketones from Ketones) and Section 113 (Esters from Esters).
Section 71
Alkyls from Hydrides
79
0.6 SnC14 , RT , 2 4 h Ph-
M e 0 w p : 8 %
SnBu3
(9:91 o:p) Chem. Lett., 1991, 133.
Yamaguchi, J.; Takagi, Y.; Nakayama, A,; Fujiwara, T.;
0
Ph
A ph
1. I-BuLi , THF -100°C + -78°C
2. soc12 , -78°C
d
-F
t-Bu
1.
h
t-BU
(9 Olah.;Wu, A.; Farooq, 0.Synthesis, 1991, 1179.
CHO
P 1)
52%
NHMe
( NHMd EtOH. reflux
2. BuLi , TMEDA ,ether
3. Etl
RT
4.2M HCl , HzO
Gray, M.; Parsons, P.J. SynLett, 1991, 729.
0
1. MeLi 58%
Quesnelle, C.; Iihama, T.; Aubert, T.; Pemer, H.; 2625.
Tetrahedron LRtt., 1992, 33,
SECTION 72: ALKYLS, METHYLENES AND ARYLS FROM KETONES
6
The conversions R2C=O -+ R-R, R2CH2, RzCHR, etc. are listed in this section.
MeVO(OEtlCI , 0 2 EtOH , 3 0 min
6
Hirao.,Mori, M.;Qh&'ro. Y.J. 018. Chem., 1990, 55, 358.
Me
90%
Compendium of Organic Synthetic Methods, Vol8
80
Section 72
Blmorsv. S.S, ;pelter, A.; Smith, K. Tetrahedron Len, 1991, 32, 4175. dioxane , 5 h 2. aq. NH4CI 12%
58%
Ind. J. Chem., 1991, 30B, 286.
Nayak, S.K.;
n
s s
MeMgI , NiClz(dppe)
* Ph
Ph-Me Yuan, T-M.; J&.
6'
T-Y. J. Org. Chem., 1992, 57, 4550. 1.
c) csz
AJ;:
84%
0 ,
2% GazC14, reflux 2.2N NaOH ,RT
(29
71)
72%
Hashimoto, Y.;Hirata, K.; Kihara, N.; Hasegawa, M.; &&&.Tetrahedron Leu., 1992, 33, 6351.
SECTION 73: ALKYLS, METHYLENES AND ARYLS FROM NITRILES Bu4Sn. MeCN hv (>300 nm)
46%
Kyushin, S.; Masuda, Y.; Matsushita, K.; Nakadaira Y.; QhsLM. ' Tetrahedron Lett., 1990, 31, 6395.
Teng, T-F.; Lin, J-13.;-Heterocycles,
1990, 31, 1201.
Section 74A
Hydrogenation of Alkenes
x
81
PhCHO , PhMe 8 0 T . 11 h
0
84%
Ph
Rvchnovskv.; Zeller, S.; Skalitzky, D.J.; Griesgraber, G. J. Org. Chem., 1990, 55, 5550. SECTION 74: ALKYLS, METHYLENES A N D ARYLS FROM ALKENES The following reaction types are included in this section: A. Hydrogenation of Alkenes (and Aryls); B. Formation of Aryls; C. Alkylations and Arylations of Alkenes; D. Conjugate Reduction of Conjugated Carbonyl Compounds and Nitriles; E. Conjugate Alkylations; F. Cyclopropanations, including halocyclopropanations
SECTION 74A: Hydrogenation of Alkenes (and Aryls)
-
Reduction of aryls to dienes are listed in Section 377 (Akene-Alkene).
d
Ph
NaTeH ,EtOH ,reflux 2.5 h
-
Ph
Barton, D.W.R.; Bohe.;Lusinchi, X . Tetrahedron, 1990, 46, 5273.
quant.
Batczewski, P.; Joule. J.A. SynM Commun., 1990, 20, 2815.
ON0*
Pd-C ,HCOOH MeOH ,70h
/
AIDer.
0””’. 0””’” +
53%
34%
Ar also reduced with other Ar-X groups
K; Vasapollo, G. Tetrahedron Left., 1992, 33,7477.
REVIEWS : “ElectrocatalyticHydrogenation Hydrogen-Activity Electrodes” Moutet. J-C. Org. Prep. Proceed. In?., 1992, 24, 309.
0 2 N - H 12%
Compendium of Organic Synthetic Methods, Vol8
82
Section 74B
"Design Concepts for Developing Highly Efficient Chiral Bisphosphine Ligands in Rhodium-Catalyzed Asymmetric Hydrogenations" SynLen, 1992, 169. Inoguchi, K.; Sakuraba, S.; &WE&.
dN2 me
SECTION 74B: Formation of Aryls
1. Et-CK-OMe ,DCE hv (253.7 nm) * 2. DCE , reflux, 4 h
50%
OH
Danheiser.;Brisbois, R.G.; Kowalczyk, J.J.; Miller, R.F. J. Am. Chem. SOC.,2990, 112, 3093.
ci
'-
11-CS-CHZOH NiClz(PPh3)~
CE C- C02Me
2 eq. PPh3 2 eq. BuLi
C02Me Bhararah, P.; Smith. E.H, J. Chem SOC.,Chem. Commun., 1991, 277. PhH , hv (Hg vapor)
Ph Olsen.;Minniear, J.C.; Overton, W.M.; Sherrick, J.M. J. Org. Chem., 1991, 56, 989.
%
hv (Hglamp/pyrex) ,I2 propylene oxide , PhH
*@@ \ /
/
Liu, L.; Yang, B.; Katz.;Poindexter, M.K. J. Org. Chem., 1991, 56, 3769.
Et
H-CECf
95%
Me Me
OH
5% Pd(OAc), ,MeCN .t 20% PPh3,5% CUI NET3,reflux, 14 h
M ~ &Me~ Me02C
~
'I'orii. S,; Okumoto, H.; Nishimura, A. Tetrahedron Lett., 1991, 32, 4167.
c OHM"
79%
Aryls from Alkenes
Section 74B
3 Et-GC-Et
NiI2 , Py ,60"C ,24 h
-
83
*tE
39%
Et
~t
6
Kong, K-C.; Chmg,L& - J. Chem. SOC., Chem. Commun., 1991, 423.
Q
VO(OEt)C12 ,Me3SiOTf EtOH , 0°C --t RT
*
Hirao.;Mori, M.; -0.
Y. Chem. Lett., 1991, 183.
OMe
82%
)$,
12, CAN ,MeOHMeCN
reflux, 8.5 h
82%
. . Honuchl.; Fukunishi, H.; Kajita, M.; Yamaguchi, A.; Kiyomiya, H.; Kiji, S. Chem. Lett., 1991, 1921.
C1 Me2HN K-;.
. .
EtOH , NEt3, heat, 2 h
Nussbaumer, P. Synthesis, 1991, 663.
0
Me
Se02-PPSE. CC4 reflux ,26 h
&ph
eMe
PPSE = trimethylsilyl polyphosphate = P205Ne3SiOSiMe3
Lee. J.G.; Kim, K.C. Tetrahedron Lett., 1992, 33, 6363.
Ce-H
83%
Me3SnSnMe3 PhNC , hv
Br Curran.;Liu, H. J. Am. Chem. SOC.,1992, 114, 5863.
96%
Compendium of Organic Synthetic Methods, VoI 8
84
Section 74C
1. [Rh(COD)C112 Bu-CC-H 2. H+ ,40"C
Padwa.;Xu, S.L. J. Am. Chem. SOC., 1992, 114,
OH 5881.
Merlic. C.A.; Bums, E.E.; Xu,D.; Chen, S.Y. J. Am. Chem. Soc., 1992, 114, 8722.
SECTION 74C: Alkylations and Arylations of Alkenes
Fotiadu, F.; Cros, P.; Faure, B.; Buono. G , Tetrahedron Lett., 1990, 31, 77.
Ph I
%-OH
Ph
1. t-BuMe2SiOTf
2 . 2 1-BuLi , THF 't-BuMe,si* -78°C + +23OC
Kim, K.D.; Magriotis. P.A. Tetrahedron Lett., 1990, 31, 6137.
Ph. 0 N= N- S02Ph /
00
=/
C02Et
,PhH ,80°c
Pd(PPh3)4, sealed t u g
Ph
OH
84%
CO2Et
Kamlgata.: Satoh, M.; Fukushima, T. Bull. Chem. SOC.Jpn., 1990, 63, 2118.
89%
Section 74C
Alkylation of Alkenes
Bp
1.Mg.THF 2. Cp.LTiCI2, CHS12
3. AIC12Et. PhMe , -78°F 4.HCI
Rigollier, P.; Young, J.R.;Fowley, L.A.;
Mea 78%
a J. Am. Chem. Soc., 1990, 112, 9441.
3 eq. PhCl , MeCN , Py Zn , NiCh(PPh3)Z *
d Ph
85
+
Ph+ph
Ph
54%
7%
Lebedev, S.A.; Pedchenko, V.V.; Lopatina, V.S.; Berestova, S.S.; Petrov, &S. Zhur. Org. Khim., 1990, 26, 1520 (Engl., p. 1312). Si(SiMe3)3+ Meb.-
-
hv ,MesSilI , 20°C
Kulicke, K.J.;Biese. B. SynLett, 1990, 91.
32)
(68
Bu3SnC1, AIBN NaBH3CN.3d *
65%
, \p +
1-BuOH ,reflux
OH
Si(SiMe3)3
OH
HO
20%
43%
Bothwick, A.D.; Caddick. S.; Parsons. P.J, Tetrahedron Lett., 1990, 31, 6911 ph
*I
J-
Me
1 . sec-BuLi, THF.-70°C
ph
Me
)AMe79%
7-
2. Me1
Barluenga.; Rodn'guez, M.A.; Campos, P.J. SynLett, 1990, 270.
PhCHO
=/ SiMeC'z,
NEt3 , 120°C
w
Ph
*
cat. PdC12(PPh3)2 Yamashita, H.; Roan, B.L.; Tanaka. M,Chem. Lett., 1990, 2175.
SiMeCl,
77%
86
Section 74C
Compendium of Organic Synthetic Methods, Vol8
Br
==/Ph , Pd(OAc)z, DMF . t
cph
TBAB , K2CO3,10O0C Br 2h L-ansky, A.; Reiser, 0.;Be Meiiere. A. SynLett, 1990, 405.
J -
HSiC13, RT
Ph
=-
/
/
92%
Ph
PhYSiC13 57% Me (64.8% ee , S)
Okada, T.; Morimoto, T.; Achiwa. K. Chetn. Lett., 1990, 999.
-
P h a F H *TiCl2(OiPr)z %FOH Ph Ph
Me
rnesirylene , MS 4A 0°C . 4 d
-
41% (84% ee)
Narasaka. K.; Hayashi, Y.; Shimada, S.; Yamada, J. lsr. J. Chetn.,1991, 31, 261. C12MeSiH. Ni* , THF ,25"C
40%
+98% ee)
SiC1,Me
1424.
92% Ni* = activated Ni, from Li reduction of NiI in THF uk. P,; Han, B-H.; Jacobsen, J.R.; Hauck, B.J. J. Chetn. Soc., Chem. Conitnun., 1991, 1. BuMgCl ,2.5% Cp2ZrClz 2. €I+
+
x>
94%
( 8 2 18 cis:trans) Knight, K.S.; Wavmouh. R. M,.I. Am. Cheni. SOC., 1991, 113, 6268.
Hatanaka, Y.; Ebina, Y.;
.I. Am. Chem, Soc., 1991, 113, 7075.
Section 74C
Alkylation of Alkenes
=?OZBn NHBoc
Carlswom, A-S.;
C02Bn
P
w
Pd(OAc)z, Bu~NCL NaHCO3, DMF
Br
87
H
B
o
c
63%
Br
J. Org. Chem, 1991, 56, 1289.
Satoh, S.; Sodeoka, M.; Sasai, H.;
& EtO2C
'
.I. Org. Chem., 1991, 56, 2278.
BusSnSiMe3, PhMe 0.1 M , Bu4NBr 3% PdC12(PPh&
Br
Li2CO3, 110°C
CO2Et
*
70%
Mori. M,; Kaneta, N.; Shihasaki, M..I. Org. Chern., 1991, 56, 3486. 5% Pdz(dba)s, PhI 2 eq. CH2(C02Et)2
PhI , DMSO , S O T Bu4NCI, NaHCO3
-
Ph
CO,Et CO2Et
82%
Larock. R.C,; Lu, Y.; Bain, A.C.; Russell, C.E. .I. Org. Chent., 1991, 56, 4589. 1.2 eq. Mg ,MeOH 2.3N HCI , 0°C
0 Dominguez, C.; Csfdcy, A.G.; IYuw,J, Tetrahedron Lett., 1991, 32, 4183.
tailors catlyst to substrate
Farina, V.;Roth, G.P. Tetrahedron Left., 1991. 32, 4243.
0
98%
88
Section 74C
Compendium of Organic Synthetic Methods, Vo18
1. MeC12SiH , CuCl Pan microwave bomb
&
TMEDA , (750 W)* microwave oven 2. HC(OEt),
N
SiMe(0EtI3
75%
Abramovitch. R.A.; Abramovitch, D.A.; Iyanar, K.; Tamareselvy, K. Tetrahedron LRtt., 1991, 32, 5251. (PhMezSi)Cu*LiCN THF , 3 0 min
0
0
quant.
Lautens. M.; Belter, R.K.; Lough, A.J. J. Org. Chern., 1992, 57. 422. SiH (SiMe&
*IDN
*
-
.Phhk
Si(SiMe3)3 81%
Kopping, B.; Chateilialoelu. C,; Zehnder, M.; Giese. B.J. Org. Chern., 1992, 57, 3994. CpzY [CH(TMS)d 14 h
-SiH,Ph
Molander. G A L ;Julius, M. J. Org. Chern., 1992, 57, 6347.
95 %
1. h v , 0 2 , DCA
H
60% DCA = 9,lO-dicyanoanlhracene
Santamaria. J,; Kaddachi, M.T.; Ferround, C. Tetrahedron Lett., 1992, 33, 781. 1. ~ - C & ~ I ~ C H ~ C H ~ M ~ C I
d n-C6H13
3% CmZrC12, THF 2.H3O+ *
G n - C , H , , (4:l
Rousset, C.J.; ,-
E:Z)
92%
Suzuki, N.; l&&&uX . Tetrahedron Lett., 1992, 33, 1965.
Section 74C
Alkylation of Alkenes
=/Bu
ICHFCOzEt
, Zn , PY , THF
*
89
Bu C H ~ C H ~ C H F C O ~ E ~
NiC12.6 HzO ,60°C Wang, Y.; Yang. Z-Y.; Burton. D.JATetrahedron Lett., 2992, 33, 2137.
TfO '
Bernocchi, E.; 3073.
73%
Pd(0Ac)z , NEt3 P(o-t0lyl)3 , DMF HO 60°C, 3 h ;Ciattini, P.G.; Morera, E.; Q&K& Tetrahedron Lett., 1992, 33,
Ph
hq,,
1 . BuLi ,-78°C 2. M q S 0 4 , -78°C -+ RT
Ph
BuTe
kq..
t
Me
93%
"Ph csPh Dabdoub. M.J. ; Dabdoub, V.B.; Comasseto, J.V. Tetrahedron Lett., 1992, 33, 2261. 1 . Pd(PPh3)d , THF PhZnCl
n-C5H1 1
2. aq. NH&l
Rossi. R.; Catpita, A.; Cossi, P. Tetrahedron Lett., 1992, 33, 4495.
Ph
TfO
NaBPh4, Pd(PPh3k
*
DMF, R T , 2 h
Ph
JrJ
Ph
73%
Ciattini, P.G.; Morena, E.; Ortar, G. Tetrahedron LRtt., 1992, 33, 4815.
cy
82% Bhatt, R.K.; Shin, D-S.; Falck, J.R.; Mioskowski. C. Tetrahedron Lett., 1992, 33, 4885.
0 0
Sakamoto, T.; Kondo, Y.;
PhI , Ag2C03, DMF c
Ph
(43% ee)
Tetrahedron Lett., 1992, 33, 6845.
62%
Compendium of Organic Synthetic Methods, Vol8
90
CJ".,,
BuMgCl , 1% Cp2ZrC12
*
Id
Section 74C
95%
(86: 14 trans:cis) Wischrneyer, U.; Knight, K.S.; Wavrnouth, R.M. Tetrahedron Lett., 1992, 33, 1135.
Ph
>-?Br Me0
B-n-C8H17
t
Ph
1
M e d 'n-CsH17 Pd(PPh3)4, dioxane 60°C, 3 q.K2CO3,16 h Abe, S.; Miyaura, N.; SUzuki. A.Bul1. Chem. SOC. Jpn., 1992, 65, 2863. OSiMe2t-Bu H
=
Me
M~
Pd(PPh3)4, THF Lizc03. Licl. reflux
*
Me
&) H
83%
OSiMeZt-Bu 91%
*Me
Liang, S.; Paauette. J..A. Acta Chem. S c a d , , 1992, 46, 597. Cp2YMe*THF,PhH (2 atm) , RT , 4 5 min
H2
*
c:d
+
c< 2%
97%
Molander.;Hoberg, J.O. .I. Am. Chem. Soc., 1992, 114, 3123.
Ph
5% Mo(CHCMe2Ph) (N[2,6-diisopropylphenyl]) (OCMe[CF312)2
PhH , 20°C, 15 min
*
bph 92%
R.H. J. Am. Chem. Soc., 1992, 114, 5426.
2. NaOH ,H2Q DiPPE = 1,2-bis(diisopropylphosphino)ethane Wescott, S.A.; Blom, H.P.; Mader. T.B.; Baker. R.T. J. Am. Chem. Soc., 1992, 114, 8863.
Section 74D
Alkylation of Alkenes
*
91
phx
OMe, 65°C
67%
(q3C3H~PdC1)2, THF * 48 h Rossi. R,; Carpita, A.; Messcri, T. Guu. Chirn. ltul., 1992, 122, 65.
Ph
SiMe2Ph
OMe
1. F3CCH21, AIBN , 85°C
Bu I
2. NaBH4, DMF O"C+ RT Cloux, R.; Kovhts, Ez. Synthesis. 1992, 409.
PhJ
d
c1
Ph
+
F,C-Bu
, Pd(0Ac)z
Ph&
*
N u ~ N110°C , , 15 h
40%
ph 57%
Hongwen, H. Synth. Commun.. 1992, 22, 2019.
Yi, P.; ;-
H Z N oI
2=/'OZEt,
37°C
- H2N
Pd(OAc)z, PhYPOTs 10 h Genet.;Blart, E.; Savignac, M. SynLeft. 1992, 715. /
SECTION 74D:
Ph
/
Conjugate Reduction of a,P-Unsaturated Carbonyl Compounds and Nitriles 1. aq. NaOH , 5 rnin Pd(0Ac)Z
\=\C02H
Ph
- \ 2. (Et0)3SiHI RT
CO2H 10 min Tour. J.Mj Pendalwar, S.L. Tetrahedron Lett., 1990, 31, 4719.
93%
0.24 [(Ph3PCuH]6 30 € 1 2 0 , RT , 1 h THF
OAc
6
M OAc
e 94%
Koenig, T.M.; Daeuhle, J.F.; Brestensky, D.M.; Strvker, J.M. Tetrahedron Lett., 1990, 31, 3237.
92
Section 74D
Compendium of Organic Synthetic Methods, Vo18
&::
0
b o &
Kiinzer.;Stahnke, M.; Sauer, G.; Wiechen. R. Terruhedron Lett., 1990, 31,3859.
0
O
1. MAD. -78°C
MAD = bis(2,6-di-t-butyl-4-rnethylphenoxy)methylaluminum
Doty, B.J.; Morrow. G.W, Tetrahedron Lett., 1990, 31, 6125.
A
(Et0)3SiH , Pd(OAc)z, aq. THF
L
OBu
O
add ester prior to silane Tour. J.M,; Cooper. J.P.; Pendalwar. S.L. J. Org.Chem., 1990, 55, 3452.
B
99%
u
n-C5H 1 1
OMOM
>90%
(70:30diastereomers) Linderman.;Griedel, B.D. J. Org. Chem., 1990, 55,5428.
CO~B d
RhCI(PPh3). THF catecholborane + -2O"C, 12 h
,C02Bn
Evans.;Fu, G.C. J. Org. Chem., 1990, 55, 5678. C- C02Et e- , PhC02H ,DMF OH
EtdNC104, (0.1 M)
82%
*L HO
CO2Et
87%
Arcadi, A.; Cacchi. S.; m; Curulli, A.; Inesi, A.; Marinelli, F. SynLett, 1990, 408.
Section 74D
Conjugate Reduction of Alkenes
93
e- ( 2e-/mol), ag. MeOH aq. KCl
Clmly - - PPV+*-Pdelectrodes
quant.
PPV = poly(pyrro1e-viologen)
Coche, L.; Ehui, B.; Limosin, D.;
m.J -CJ. Org. Chem., 1990, 55, 5905.
H2.lh
CHO
,CHO
h.. M q
4
quant.
&sNl'dClz cat* Fe
&s- Ar
Ar=p-Me-phenyl
Ali, H.M.; Naiini, A.A.; Brubaker, C.J. Jr. Tetrahedron Lett., 1991, 32, 5489. 1. NaSeH , 5 0 T , 3 h , EtOH 2 . 2 N HCI c
Ph
0
Ph&Me 84% Nishivama. Y. : Yoshida, M.;Ohkawa, S.;JIamanaka. S . J. Org. Chem., 1991, 56, 6720. CO,H
cHo 2.HzO *CHO 73% Tanaka. K.; Matsuura, H.; Funaki, I.; Suzuki, H. J. Chem. SOC.,Chem. Commun., 1991, 1145. Bu
1 . 7 eq. CH2N2, cat. Pd(0Ac)z
%
2. NaBOq.4
ether
H70,
O % Fontani, P.;
.
; Vaultier, M.;
fi''~,
reflux, 50 mip
Bu
dioxane - HzO
76-82%
Maas&, Synthesis, 1991, 605.
t-BuSOzCHzLi ,THF n-C8H 17
2% Ni(acac)z ,reflux
m
Gai, Y.; Julia M,; Verpeaux, J-N. SynLett, 1991, 56, 269. PhzS=CHz , Cu(acac)z
NaH,THF
*
Cimetikre, B.; Julia. M,Synktt, 1991, 271.
crf^
Ph
SMe
1. BuLi ,THF -78°C -+ 0°C 2.MeOH
0
86%
'8
*
82%
Krief.;Batbeaux, P Tetrahedron Lett., 1991, 32, 417. 1. Me3SO+I-, NaH 2. r-BuOK, aq. ether
dMr r l ~ OMe -
BnO
65%
[rn-C8H17
Rodriaues. K.E, Tetrahedron Lett., 1991, 32, 1275.
t
Q"4CO2H
BnO
88%
Section 74F
Cyclopropanations of Alkenes
2::;’ 8 COzMe
=/
Me0
C0,Me
Me0 i- +C02Me
THF.6.5OC
+
113
54)
(46
PPh3
64% 39970
74)
(26 : Merndon. J.W,; Tumer, S.U. J. Org. Chem., 1991, 56, 286. Me
~ C - H M,ok Cr(CO)s , sioz ~ C - H decane ,63OC, 3 h
Me02C Meo2c
Ph-
OH
(39%ee)
Chem. Lett., 1992, 61.
55%
116
Compendium of Organic Synthetic Methods, Vo18
Section 75
Denmark.,Edwards, J.P. SynLerr, 1992, 229.
SECTION 75:
ALKYLS, METHYLENES AND ARYLS FROM MISCELLANEOUS COMPOUNDS
-
PdC12(PhCN)2 ,xylene Ti(OiPr)4
C
I
W
C
Miura. M,; Hashimoto, H.; Itoh, K.; Nomura, M. Chem. Let?., 1990, 449. PhMgBr , ZnBr2
l 76%
(N1Ph
kHO
6HO
Brown, D.S.; Hansson, T.; Lev. S.V. SynLett, 1990,48. Brown, D.S.; Charreau, P.; Lev. S.V. SynLert, 1990, 749 [with ZnC121.
Yanagisawa, A.; Nomura, N.; Yamamoto, H, SynLett, 1991, 513.
87%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 6 PREPARATION OF AMIDES
SECTION 76: AMIDES FROM ALKYNES
H-
ci
'-
CMe3
1. BuLi , THF , -60°C 2. Me3SiCI. -20°C + RT
3.55"C. PhZNH , 11 h*
heating after 2. leads to ketenes
M e 3 S i T 0
NPh, quant.
Valentl, E.; Pericas, M.A.; Serratosa, F. J. Org. Chem., 1990, 55, 395.
SECTION 77: AMIDES FROM ACID DERIVATIVES
Corriu. R.J.P.; Lanneau, G.F.; Perrot-Petta, M.; Mehta, V.D. Tetrahedron Lett., 1990, 31, 2585. NEt3 , MeCN
x:
H02C
*
n
LJ
n7
n-C6H, 1
CI EtO' p*'c, "
1114, I"
"L
OR N i l
Kim, C.W.; Chune, B.Y.; Nam Kung, J-Y.; Lee, J.M.; Kim.
S, Terrahedron Lett., 1990, 31, 2905.
HN(SiMe&, MeOH DMF, RT, 16 h
* Z:-H
0 Davis. P.D, ; Bit, R.A. Tetrahedron Lett., 1990, 31, 5201.
0
93%
Compendium of Organic Synthetic Methods, Vol8
118
Section 7
Manhas. M.S. ; Ghosh, M.; Bose, A.K. J. Org. Chem., 1990, 55, 575.
N’ N’ Me
0
Pandhi, S.B. J. Org. Chem., 1990, SS, 2196.
COOH
OL
’
nN 0
NEt3 , CHzC12
Me
sharma. S.D;
Me
PhO
P h O y
pyrrolidine , CBr4, NEt3 PPh3 ,RT , 15 min
ph Me
Me
good yield
&’ \
Einhorn. J.; Einhom, C.; Luche, J-L. Synth. Commun., 1990, 20, 1105.
P h d
reflux ;
(15:l &:trans)
OMe
Mashava, P.M.; Guan, X. Tetrahedron Lett., 1992, 32, 581.
CH3COOH
n-C&lsNH;!, PhH Ph3SbO , P4S 10
ACNH-~I-C~HI~
90% 40°C,5h Nomura.; Nakano, T.; Yamada, Y.; Matsuda, H. J. Org. Chem., 1991, 56,4076.
R U ~ ( C O )Ph-NOz ~~,
C02H
180°C, 8 h
-
Nahmed, E.M.; Jenner. G, Tetrahedron Lett., 1991, 32, 4917.
NHPh
51%
89%
Amides from Aldehydes
Section 79
U'ySh-PPh3 MeCN ,reflux
119
c
(CH2)6 Shi, Y . Tetrahedron Lett., 1992, 33, 943. Boc
1. H-N,
0 II
OSiMezt-Bu
c
0 PhA N- OH
DMAP , MeCN , 5 h 77% 2. TFA ,CH2Ci2,0°C H 6h Altenburger, J.M.; Mioskowski. C.;dOrchymont, H.; Schirlin, D.; Schalk, C.; Tamus, C. Tetrahedron Let(., 1992, 33, 5055.
PhAC1
SECTION 78: AMIDES FROM ALCOHOLS AND THIOLS CoC12, MeCN , Ac20 80"C, 15 h
-L NHAc
70%
Nayyar, N.K.; Reddy, M.M.; IgbaIJ, Tetrahedron Left., 1991, 32, 6965.
SECTION 79: AMIDES FROM ALDEHYDES
-
NBS , AIBN CC14, BuNH2
O C H O
p o N H B u
80%
Mark6.;Mekhalfia, A. Tetrahedron Left.,1990, 31, 7237.
.
1. BnOKNSO -25°C
-CHO
BF3;0Et2, CHzCI2
2. Et3SiH
Alexander, M.D.; Anderson, R.E.; Sisko, J.;
t
-NHCbZ 64% J. Org. Chem., 1990, 55, 2563.
120
Section 79
Compendium of Organic Synthetic Methods, Vo18
Msov +
Ms
@ cB(0H)2 HO
’ N,
H
Br
Na2CO3 Pd(PPh3)4
DME , reflux
/
L O
Siddiqui, M.A.; Snieckus. V, Tetrahedron Lett., 1990, 31, 1523.
*
0 L O
1. PhNH2 ,HC1, KCN 2.1-BuOK , 0 2 ,THF
PhCHO
76%
/
RT
-
49%
Chuang, T-H.; Yang,C-C.; Chiang, C-J.; l%agJ&L SynLRtt, 2990, 733.
Ph
CHO
2 eq. SIC13 ,MeCN 2 H 2 0 , CH2C12,lO h Ph b
I N H C O z M e 59%
Elm0rSv.s.s.; Nour, M.A.; Kandeel, E.M.;Pelter, A. Tetrahedron Lett., 1991.32, 1825. 1. N(SnMe3)j 2. t-BuPh2SiCl
0
CHO 3.
b
)=(:;
kN*
0
65%
SiPh2t-Bu
Busato, S.; Cainelli, G.; Panunzio, M.; Bandini, E.; Martelli, G.; Spunta, G. SynLett, 1991, 243.
SECTION 80:
AMIDES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 81: AMIDES FROM AMIDES Conjugate reductions of unsaturated amides are listed in Section 74D (Alkyls from Alkenes). 1. sec-BuLi 2.DMF 3. HCI
Boc Clark. R.D.; Muchowski, J.M.; Souchet, M.; Repke, D.B. SynLelt, 1990, 207.
121
Amides from Amides
Section 81
1. Na, THF
coupling occurs in some cases
Karman, R.;Fry, J.L. Tetrahedron Lett., 1990, 31,941. 10% Pd(OAc),
Me P 4 B ' Na'
0
30%
70%
&igg&; Dorrity, M.J.; Malone, J.F.; Sridharan, V.; Sukirthalingam, S. Tetrahedron Lerr., 1990, 31, 1343.
v
NHz
H
1. IIg(OAc)s,DMF
K
MeOH N OMe 2. N3S , DMF 0 12h 91% 0 new Hofmann rearrangement Jew. S ; Park, H.G.; Park,H-J.; Park,M.; Cho, Y. Tetrahedron Lett., 2990, 31, 1559.
0 EtOA NH, Wachter-Jurcsak,N.;
1. t-BUOH 2. NaOH 3. BEt3 ,65"C,6 h
*
4. aq. NaOH
0 EtOlcNHEt
8048% Tetrahedron Lett., 1990, 31, 5261.
Na2(P4SloO), THF .25"C 2h
-
S
L N H
88%
Brillon.D.ynrh. Commun., 2990, 20, 3085.
0
HJ- NMePh
w,Kojima, A:,
Se(AIMe32, PhMe-THF 40°C , 4 h
b
H
P
Nakajima, T.; Suga, S. SynLett, 1991, 105.
NMePh
91%
Section 8 1
Compendium of Organic Synthetic Methods, Vol8
122
(82 18) Polniaszek.; Belmont, S.E.; Alvarez, R. J. Org. Chem., 1990, 55, 215.
90%
SnC14, -23°C 1.5 h
80% Org. Chem.. 1990, 55, 1447. Fisher, M.J.; Overman.L.E.,
(CF3C0)20, RT CH2C12,5 h
he
Me
87%
Masuda, R.; Hoio. K;Ichi, T.; Sasano, S.;Kobayashi, T.; Kuroda, C. TetrahedronLett., 1991, 32, 1195.
Ph
Me
MezS(=O)CN- , DMSO 2% *
w N
S02Ph
SO,Ph
r- "
t-lMe
51%
Ph
Nadir.;Sharma, R.l.; Koul, V.K. J. Chem. Soc., Perkin Trans. I, 1991, 2015.
0-
:loti
Me
Bu3SpnhHH' AIBN
c
&o H Me
+
O7lo Me
73% (3aMe:3PMe 6:l) M i b s h i . H.: Nakamura, N.; Sato, T.; Takeuchi, M.; &eda. M, TetrahedronLetl., 1991, 32, 1725.
-ins.
123
Amides from Amides
Section 81
OMe R* = (-)S-phenylmenthyl
D.L; Badawi, M M .Telrahedron Lett., 1991, 32,2995.
Bn
1. LDA 2. BnBr
% 0
0
*
ph8-'*\-0
63%
h.*'L O (1.8:l trans:cis)
Baldwin. J.E,; Moloney, M.G.; Shim, S.B. Terrahedron Lerr., 1991, 32, 1379.
Ac
BuzSnCl . NaBHqCN
&
N.
1)
(4
90%
Clark,A.J.; Iones.; McCarthy, C.; Storey, J.M.D. Tetrahedron Lelt., 2991, 32, 2829.
Me NH2
0
H
PhCHO , PPA ,35"c
74%
72 h
H Marson.;Grabowska, U; Walgrove, T.; Eggleston, D.S.; Baures, P.W. J. Org. Chem., 1991, 56, 2603.
I
0
Y
0
NsPh
0 ~ 1 ~ 1 3
*
'),"*ph
0
m.A.; Seki, K.; Matsuda, H. J. Org. Chem., 1991, 56, 2684.
quant.
124
Compendium of Organic Synthetic Methods, Vo18
.
0
1. sec-BuLi TMEDA
THF , -78.C 2. B(OMe)3
N(iPr)L
Section 8 1
3. H30+ Br , Pd(PPh3)d
4.
aoMe
DME
81%
Me0
aq.Na2CQ
No, B.I.; Kandil, A.; Patil, P.A.; Sharp, M.J.; Siddiqui, M.A.; J. Org. Chem., 1991, 56, 3763.
*.
V. ; Josephy, P.D.
B y S n H , AIBN PhH , 8OoC m
81%
cisltrans)
Curran. D.P.; Abraham, A.C.; Liu, H. J. Org. Chem, 1991, 56, 4335. PdC12(PPh3)2, DMAC
H $ (
/
DBU95 , 115OC, psi CO 5.5 h
.r
h'l$-zf
/
0
DMAC = N,N-dimethyl acetamide Perm. U;Turner, S.R. J. Org. Chem., 1991, 56, 6573. H2
0 4 NH,
(300 psi)
CO (900 psi)
HRh(CO)(PPl;;h 2 eq. dppb ,80°C
Bra
+Meh
Qo
Y
H
40 h
63%
H
2)
(98
O
88%
QiimaL. Korda, A.; Shay, W.R. J. Org. Chem.. 1991, 56, 2024.
Me- N
Bu3SnH. AIBN PhH ,reflux ,0.02 M
--
Me-$.
Me0
Hart.; Wu, S.C. Tetrahedron Lett., 1991, 32,4099.
p
0 Me0 (I:]
95%
a$)
Section 81
Amides from Amides
1. 5% RuC12(PPh& , 2 h 140°C
CCl,
oA
N--(=
H
125
2. B y S n H , PhMe , 1 h reflux
Me
* On M N i e
H 47% Nagashma, H.; Wakamatsu, H.; Ozaki, N.; Ishii, T.; Wafanabe, M.; Tajima, T.; Itoh.K.. Org. Chem., 1992, 57, 1682. 1. BuLi , DABCO 2. 3 eq. Cu(0Ac)z
0
COzt-Bu
Kawabata, T.; Minami, T.;
OMe J. Org. Chem., 1992, 57, 1864. Bu3SnH, AIBN PhH , reflux
70%
Me Keusenkothen, P.F.; Smith. M.B. Tetrahedron, 1992, 48, 2971.
1 . LDA 2. BnBr
+ Bn 1)
Kimura, K.; Murata, K.; Otsuka, K.; Ishizuka, T.; Haratake, M.; 1992, 33, 4461.
MEOX = tetrakis[rnethyl 2-oxazolinone4(S)-carboxylate]
(71 % ee)
76%
Tetrahedron Lett.,
(80% ee)
h y . k M & ; Protopopova, M.N.; Winchester, W.R.; Daniel, K.L. Tetrahedron Lett., 1992, 33, 7819.
Compendium of Organic Synthetic Methods, Vo18
126
fi:
fiMe
Ph2NN0, PhH , 3 h
0
reflux
NH2
Section 81
O
51%
H
!XhkLQ.; Pem, S.T.; Toske, S.G. Tetrahedron Lett., 1992, 33, 433.
Kotsuki.; Iwaski, M.; Nishizawa, H. Tetrahedron Lett., 1992, 33, 4945. Me
-0\ 1
Pb(OAc)3
NaH , C12CH2-DMF 70°C, 7 h
0
0
86%
L@ez-Alvarado, P.; AvendaAo, C.; Menkndez, J.C. Tetrahedron Lett., 1992, 33,6875.
H
k0'
CH2CC13
1. PhI(COCF3)2, CH2C12 0°C , 2.5 h 2 . 3 eq. Zn dust, 12 h AcOWacetone ,RT
H
70%
Scartozzi, M.; Grondin, R.; Leblanc. '6, Tetrahedron Lett., 1992, 33, 5717.
.
j+
1 . PhLi , CuBr*SMQ THF
t-BuO"'ny
o
Ac
Kwt, W-J.;
Me3SiCI ,-78°C + RT
2. MqNH , DMF , RT , 2 8 h 3. 3 q . e S i M q 3 eq. BF3*OEt2, 18 h , RT CH2CI2
?Lo
47%
Tetrahedron Lett., 1992, 33, 7969.
-;
c1
0
Bu3SnH ,AIBN
PhMe ,reflux
'
Me
63%
Me
Sato, T.; Nakamura, N.; Ikeda, K.; Okada, M.; Ishibashi, H.; I ls&. Trans. I, 1992, 2399.
8% Me
J. Chem. SOC.,Perkin
127
Amides from Amines
Section 82
BuBr , TBAB , KOH
Ph y NH2 0
P ~ ~ N H B ~
~
71%
80°C
0 Loupy, A.; Sansoulet, J.; Dfez-Barra, E.; Carrillo, J.R. Synth. Commun.,1992, 22, 1661.
Ph
p"k
3.3 eq. Bu3SnH
S P ~ P m e , MBN
Ph
c
14.5 h
0
Me
Me
Sato, T.; Machigashira, N.; Ishibashi, H.;
Heterocycles, 1992, 33, 139.
,PhMe
C1-CSC-H
* H---$
reflux ,80 h
0
90%
0
Gesson, J.P.; Jacquesy, J.C.; Rambaud, D. Bull. SOC.Chim. Fr., 1992, 129, 227. 1. PhMe , PhLi
CH20SiMe2t-Bu 2."-C5H11Br H Keusenkothen, P.F.;
O
.-
G CH,0SiMe2t-Bu
~-C5H11
Synth. Commun., 1992, 22, 2935.
75%
SECTION 82: AMIDES FROM AMINES 1. P C ~ 5 Bum2
~
Y N H B u
2.2
0
77%
C02H Cabral, J.; Laszlo.:Montaufier, M-T.; Randriamahefa, S.L. Tetrahedron Lett., 1990, 31, 1705.
Bai. D,; Bo, Y.;Zhou, Q. Tetrahedron Lett., 1990, 31, 2161.
128
Compendium of Organic Synthetic Methods, Vol8
H20, 100"C,0.3h
NH2
Ph
(Ac0)zNOMe
*
Section 82
Ph*NHAc
99% N-methoxy diacetamide - a new acetylating reagent many amines are acetylated at RT Kikunawa.;Mitsui. K.; Sakamoto, T. Tetrahedron Lett.. 1990, 31, 243.
0:
[Rh(OAc)213 , PPh3 H2/CO, EtOAc ,20 b autoclave ,400 psi 50°C
* Me
H
95%
Anastasiou, D.; k k s nn. W.R. Tetrahedron Lett., 1990, 31,4795,
ph LNH2
Cp2Ti(02CiPr)2, THF reflux. 24 h
' 82% H Recht, J.; Cohen, B.I.; m m a n . AS,; Kohn. L Tetrahedron Lett., 1990, 31, 7281.
H
OH
84%
m; Oda, T.; Sugahara, T.; Masui, Y . J. Org. Chem., Z990, 55, 1744.
*> Vn
Me Chamchaang, W.;
1. LiI
2. Ni(C0)d
3. I2 workup
Lr
'yo
Me
50%
A.R. J. Org. Chem., 1990, SS, 2943. 1. (EtqC),O,
2. Pb(OAc)i, AcOH
45%
21%
Lenz.; Costanza C.; Lessor, R.A.; Ezell, E.F. J. Org. Chem., 1990, 55, 1753.
Section 82
h i d e s from Amines
129
Cho, I-S.; Tu, C-L.; Mariano. P.S. J. Am. Chem. SOC., 1990, 112, 3594. montmorillonite , KSF PhMe ,reflux, 13 h
N-OH
59%
Me
Me
Synfh. Commun., 1990, 20, 3253.
1.LiAlH4 , ether, 0°C 2. AQO, Py , RT
* O N H A c
0
SynLett, 1990, 677.
SbCl5 , AgSbF6, MeCN reflux, 3 h
N.
H'
OTMS
Mukaiyama, T.; Harada, T. Chem. Left., 1991, 1653.
>=
OAc
Fembdez, S.; MenCndez, E.;
Me 89%
Synthesis, 1991, 713. 1. MeCkN-0
Ph.
0
Ph
NA
PhlCNHPh
2. f-BuOK , THF 3. H20 Aitken. R.A,; Raut, S.V. SynLett, 1991, 189.
NH, Naota, T.;
'
77%
0
c.-l'
piperidine, THF ,25"C 30 min *
N'
76%
RUHz(PPh,), , DME , 3 h benzalacetone , 140°C
SynLett, 1991, 693.
w
Go H
51%
59%
130
Compendium of Organic Synthetic Methods, Vol8
wTph
Section 82
0
1. M ~ O~A 1 N E, t 3 , MeOH c
2.TMSOTf
modified Pictet-Spengler
Cheung, G.K.; Earle, M.J.; Fairhurst, R.A.; M e V . H.; Shuhaibar, K.F.; Eyley, S.C.; Ince, F. SynLett. 1991, 721.
M e 0 OMe
M
e
6 OH
Y-Ph 1 1 ooc Me Bauenneister, S.; Gows, I.D.; Straws, H.F.; 1991, 561.
Mex
Me 0
-
-vC'ph
82%
Me
J. Chem. SOC.,Perkin Trans. I,
KMnO4, aq. MeCN
Ph
~
phb N. t-Bu
t-BU
73%
'
kN.H
0
Larsen, J.; Jargensen. K.4,; Christensen, D. J. Chem. SOC., Perkin Trans. I, 1991, 1187.
NH2
ethyl ,40T - bulvrate . lipase SP 382.1 h
hindered m i n e s gives lower yields
-NHAc
-
.r
quant.
Djeghaba, Z.; Deleuze, H.; Lk Jeso, B.; Messadi, D.; Maillard, B. Tetrahedron Lett., 1991, 32,761.
-"O .H
EtsSiH , RT ClCOzMe
t
overnight
C0,Me
OH
Wu. P-L,; Sun, C-J. Tetrahedron Lett., 1991, 32, 4137.
74%
PhSO&l, B u g 1 CHzClz, 25°C
S0,Ph
76%
Sheu, J.; SUWLMJL ; Oeschger, T.R.; Satchell, J. Org. Prep. Proceed. lnt., 1992, 24, 147.
Nomura. R,; Hasegawa, Y.; Ishimoto. M.; Toyosaki, T.; Matsuda, H. J. Org. Chem., 1992. 57, 7339.
131
Amides from Esters
Section 83
Ph
I
Me Wang, M.D.; m
CO~(CO)S , CO (54 a m ) PhH , 7 2 h
J
gr
*
. Am. Chem. SOC.,1992, 114, 7018.
,OH
56%
he
T E A , [Et02CCH2CI/Znl
Mulengi. J.K.; Fauni, N. Bull. SOC. Chim Belg., 1992, 101, 257
3 eq. MesSiCl, 6 eq. DMF 3 eq. imidazole , RT
84%
H
Berry, M.B.; Btagg, J.; Craig, D.; Willis, M.C. SynLett, 1992, 659.
CHO
SECTION 83: AMIDES FROM ESTERS MeHNCHO ,THF
OMe
100°C. NaOMe15 ,MeOH min
90%
d N H M e
Jandmann. G.E. J t ; Munson, H.R. Jr.; Gero, T.W. Synth. Commun., 1990, 20, 1203.
28)
(72
Cinquini, M.; C o d , F.; Cozzi, P.G.; Consolandi, E. Tetrahedron, 1991, 47, 8767.
0
(TMS)zN-SnNHBn hexane , RT , 12 h
Ph \Ic OMe Wang, W-B.;
J. Org. Chern., 1992, 57, 6101.
NHBn
99%
Compendium of Organic Synthetic Methods, Vol8
132
porcine pancreatic lipase. t-amyl alcohol, pH 7.8
H
h
Me
w
6d
NHZ
Section 85
'U-O40%
Gutman.;Meyer, E.; Yue, X . ; Abell, C. Tetrahedron Letr., 1992, 33, 3943.
r e - B a u d e t . ; Morere, A.; Dias. M. Tetrahedron Lett,, 1992, 33,6453, Ph-N=C=O, THF , 8 h Pd(PPh3)4, RT
OK0
70%
0
0
Tamaru. Y,;Bando, T.; Kawamura, Y.;Okamura, K.;Yoshida, Z.; Shiro, M. J. Chem. Soc., Chem. Commun., 1992, 1498.
SECTION 84:
AMIDES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDlTIONAL EXAMPLES
SECTION 85: AMIDES FROM HALIDES AND SULFONATES
&
1. 2 BuLi , -78°C
Ph>S02NH2 72% (13%ee)
N- S02Me 2'BnBr
Davis. F,A,; Zhou, P.; Lal, G.S. TetrahedronLett., 1990, 31, 1653.
II -
1
ID..
\
0-
L . .
2. NEt3 ,reflux
Flvnn.,Zabrowski, D.L. J. Org. Chem., 1990, 55, 3673.
59%
Section 87
133
Amides from Ketones
\r B~
Nf33, n-C6H14, NHEt2 C02(CO)8 ,50 atm CO
b3
Br
lOO"C, 48 h NEt, 87% wivashita. A,; Kawashima. T.; Kaji, S.; Nornura, K.; Nohira, H. Tetrahedron Lett., 1991, 32, 781.
SECTION 86: AMIDES FROM HYDRIDES
Q
80°C. 18 h 2.3 eq. Zn , 2 h AcOH + acetone 3. A c ~ OPy , , RT CH2C12.18 h
*
~
N
H
A
85%
Lehlanc.;Zamboni, R.; Bernstein, M.A. J. Org. Chem., 1991. 56, 1871.
with addition of CO, get a low yield of the aldehyde
Olah.;Wang, Q. Synthesis,
Z992, 1090.
SECTION 87: AMIDES FROM KETONES SS ,NH4OAc Py ,reflux
6
You.;Zhou, H-Y.; Wang, Q-2.;Lei, X-H. Org. Prep. Proceed. Int., 1991, 23,435.
Me
*'
Me
Ph
Phx N H ~
2.MPCA * 3. hv (254 nrn)
Me
MPCA = monoperoxycamphoric acid AuM. L;Hamrnond, M.; Gherardini, E.; Takusagawa, F. J. Org. Chem., 1991, 56, 499.
~
134
Compendium of Organic Synthetic Methods, Vo18
B Q
(NH4)zC03, PhH H-CH2SH El-Zohrv. M.F. Org. Prep. Proceed. Int.. 1992, 24, 81.
Section 88
65%
H
2 eq. n-Ca13N3 2.5 eq. TiC14, 16 h CH2C12,O"C + RT
-
b
80%
AuM. L;Milligan, G.L.; Mossman, C.J. J. Org. Chem, 1992, 51, 1635.
Aube.;Milligan, G.L. J. Am. 0
Chem. SOC.,J99J. 113, 8965.
NaBH4, NiC12.6 H 2 0
+
1
quant.
PhlC N3 MeOH ,lO°C, 5 min Ph NH, B o . H.S.P,; Reddy, K.S.;Turnbull.;Borchers, V. Synth. Commun., 1992, 22, 1339. 1. CHzI2 ,Zn , TIC14 2. C102SNCO
P
h
q
Ph
3.RT,12h
SO&l Black. T.H,; Olson, J.T.; Abt, D.C. Synth. Commun., 1992, 22, 2729. REVIEWS:
"Carbon-Carbon Bond Cleavage by the Haller-Bauer and Related Reactions" Gilday, J.P.; Paauette. L.A, Org. Prep. Proceed. Int., 1990, 22, 167.
SECTION 88: AMIDES FROM NITRILES SH
NH3' C1
Ph
A C=N -
HCI(g) ,-78"C 85%
0
new Pinner type reaction Lee, Y.Y.;Lee, J.K. Tetrahedron Lett.. 1990, 31, 1169. Lee, Y.B.; Goo, Y.M.;
Section 88
Amides from Nitriles
1. MeAI(CI)NH2 ,80°C
Ph-
CkN
P
/
PhMe
135
h
y NH2 NH
93%
2. H2O WniDati. R.S. Tetrahedron Lett., 1990, 31, 1969.
1. (MaSi)zSe, 2.2 BFyOEt2 CH2C12, 6OoC, 8 h
PhCN
&
2. aq. N ~ H C Q
Shimada, K.; Hikage, S.; Takeishi, Y.;-a.
66%
Y, Chem. Left., 1990, 1403.
NaB03.4 H20, H2O dioxane.89°C.65hb H 2:*rB
65%
(39% "purified') Reed, K.L.; GuDton. J.T.; Solarz, T.L. Synfh. Commun., 1990, 20, 563.
-
NazC03*3 H 2 0 2 , acetone
Ph-CkN
H20,SO"C
94%
Kabalka. G.W, ; Deshpande, S.M.; Wadgaonkar, P.P.; Chatla, N. Synth. Commun., 1990, 20, 1445.
Ph 7 CN
1. P ~ S ~Na2S O , ,THF ,20°C
2.H2O
*
73%
Ph-lfNH2
S
B r i l l o n . S y n r h . Commun., 1992, 22, 1397
Ph-CZN
(Me$i)zS , NaOMe , DMEU 30°C
w
80%
DMEU = 1,3-dimethyl-2-imididinone
Lin,
P-Y.;Ku, W-S.; W. M -J, Synthesis, 1992, 1219.
SECTION 89: AMIDES FROM ALKENES l.O=C=N-S02CI , CC4 0°C -) 25OC
g
ySiMe3 2. aq. Na2S03
c-
SiMe,
0
Colvin. E.W,; Monteith, M. J. Chem. SOC.,Chem. Commun., 1990. 1230.
60%
Compendium of Organic Synthetic Methods, Vol8
136
Me&
SMe3
Me
ClS02NC0, CH2C12 NazS03, NaHCO3 -20°C , 4 h
Section 89
2
Nativi, C.; Perrotta, E.; Ricci, A.; U&hJl, ' Tetrahedron Leu.,1991, 32, 2265. 1. C12NC02t-BuIPhMe 50"C, 6 h 2. Zn ,NHdOAc, 0°C dioxane , 1 4 h Tetrahedron Lett., 1991, 32, 4045.
Orlek, B.S.;
Dkuma. K,; Komiya, Y.; Ohta, H. Bull. Chem. SOC.Jpn., 1991, 64, 2402.
(26:l dr , S)
Whitesell., Yaser, H.K. J. Am. Chem. Soc., 1991, 113, 3526.
&nn.
D.L.; Zabrowski, D.L.; Nosai, R. Tetrahedron Lett., 1992, 33, 7281.
SECTION 90:
-Co2Me
AMIDES FROM MISCELLANEOUS COMPOUNDS Bu$nH, PhMe AIBN ,75"C
SCN
40 min
Bachi.;Denenmark, D.J. Org. Chem., 1990, 55, 3442.
H - N S F
94%
Section 90
Amides from Miscellaneous
NO,
aNHc
-
P ~ C I ~ - H ~ P V2040 ~MO~ 3 eq. CO ,MeOH ,DME
137
96%
Izllmi.;Satoh, Y.; Urabe, K. Chem. Lett., 1990. 795.
Kobs, U.; Neumann. W.P.Chem. Ber., 1990, 123, 2191.
N: N 0
BuLi , CHzClz
Bu t-BuO~C-N'
H t-BuQC- N
Nqo+
c
H
W 26)
(74
yamam0to.y.;Yumoto, M.; Yamada, J. Tetrahedron Lett., 1991, 32, 3079.
25%
Basha. A; Ratajczyk, J.D.; Brooks, D.W. Tetrahedron Lett., 1991, 32, 3783.
Et
BnOH , HCI/CH2C12
-N=C=O
Et
RT,Sh
NHCbz
92%
Benalil, A.; Roby, P.; Carboni, B.; Vaultier. M. Synthesis, 1991, 787. 1. PhSnMe3 ,20°C
ClSO,-N=C=O Arnswald, M.;
2. H 2 0 Chem. Ber., 1991, 124, 1997.
PhSO2NH2
82%
Zeolite (H-Y) , PhMe reflux, 24 h
M MeSe 5 = N a Reddy, T.I.R.; Bhawal, B.M.;
* MeS'No
H Tetrahedron Lett., 1992, 33, 2857.
70%
88%
Section 90
Compendium of Oiganic Synthetic Methods, Vol8
138
BuHN
Rh(C1)CO
1. P(OMe)3 , HCI
CHZCLZ -78°C 2. P(OMe)3 ,MeOH -78°C - RT
Ph
90%
Ph
Krafft.;Yu,X.Y.;Milczanowski, S.E.; Donnelly, K.D. J. Am. Chem. SOC., 1992. 114, 9215.
p-.
EtO' EtO
Ph
S
1. NaH ,THF
"fi
H
t
,
46%
t s 8
reflux, 4 h
Okurna.
K.; Ikari, K.;Ohta, H. Chem. Lett., 1992, 131.
REVIEWS:
"Organometallic Carboxamidation" Org. Prep. Proceed. lnf., 1990, 22, 271 w t a s . C.G.;
SECTION 90A: PROTECTION OF AMIDES n-C3H7CHO, p-TsOH , PhMe 70%
H
1. Et30' BF4
*
9
0
?
2.H20 67% 3.pH8 Smith, M.B.; Wang, C-J.; Keusenkothen, P.F.; Dembofsky, B.T.; Fay, J.G.; Zezza, C.A.; Kwon, T.W.; Sheu, J-L.; Son, Y.C.; Menezes, R.F. Chem. Lett., 1992, 247.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 7 PREPARATION OF AMINES
SECTION 91: AMINES FROM ALKYNES 5% PdC12(MeCN)2 MeCN-H20 , 5 h
n-C8H,fCr C\
NH,
reflux
*
Qn-C8H17 67%
Fukuda, Y.; Matsubara, S.; Utimoto. K. J. Org. Chem.. 1991, 56, 5812.
Fukuda, Y.; Ytimoto,
Ic.Synthesis,
1991, 975.
SECTION 92: AMINES FROM ACID DERIVATIVES
PhCOOH
1. SOC12 ,reflux 2. HOSA , PhMe , reflux 3.H+
c
67%
PhNH2
IIOSA = hydroxylamine 0-sulfonic acid Wallace. R.G,; Barker, J.M.; Wood, M.L. Synthesis, 1990, 1143.
lepidine ,hv Ph(02CCF3), 2.5 h 0°C -+ RT
Toao. H,; Aoki, M.; Yokovama. M. Tetrahedron Lett., 1991, 32, 6559.
52%
Compendium of Organic Synthetic Methods, Vol8
140
Section 94
SECTION 93: AMINES FROM ALCOHOLS AND THIOLS
Tf
MeNHTf ,THF
PhboH
Ph,
DEAD,PPh3
N.
Me
Edwards.;Stemerick. D.M.; McCad~y,J.R. Tetrahedron Lett., ZnN6.2 Py , PPh3, RT iPr02CN=NCO*iPr
OH
M
~
PhMe
70%
1990, 31, 3417.
~
+ 81%~
~
N3
Synthesis, 1990, 130.
Viaud, M.C.;
1. Tf20 , CHzClz , NEt3
-15OC
2. piperidine ,MeCN reflux, 12 h quant.
some mines required 10 kbar of pressure
Kotsuki. H.; Kibayashi, S.; Suenaga, H.; Nishizawa, H. Synthesis, 1990, 1145, 1147. 1. MsCl ,NEt3 ,THF 2. c-C&IIlNH2 NEt3
H.
I
p h q NMez Me
*
PhH ,reflux
4)
,hqNMe2
50%
Me
Dieter. R.K,; Deo, N.; Lagu, B.; Dieter, J.W. J. Org. Chem., 1992, 57, 1663.
SECTION 94: AMINES FROM ALDEHYDES OHC-CHO
c
PhNH,
NHPh
HFe(C0)i , 1M KOHEtOH 52% CO , R T ,24h Shim.;Kwon, Y.G.;Doh, C.H.; Kim, H.S.; Kim, T.J. Tetrahedron Leu., 1990, 31, 105.
>
1. TsN=S=O, CHzCl2
CHo
Sisko, J.;
* 2. MeMgBr
J. Org. Chem., 1990, 55, 393.
HNHT:3S
Section 94
2
Amines from Aldehydes
J(NN
fi
+
N
1. BnN€12,20°C H20
CHOCHO 2. NaBH4
H
141
-0 N
Bn
Katritzkv, A.R,; Fan, W-Q. J. Org. Chem., 1990, 55, 3205. Kauitzkv. A.R,; Fan, W-Q.; Fu, C. J. Org. Chem., 1990, 55, 3209. 1. TsNSO , SnCI4, PhH O"C+ RT
EtCHO
91%
I
NHTs
2- &SiMe, El Ralbovsky, J.L.; Kinsella, M.A.; Sisko, J.; Weinreb. S.M. Synth. Cummun., 1990, 20, 573. 95%
Me*
1. PhNH2, PhH , reflux 2. NaBH3CN, MeOH
r/' N,) CHO
THF,5NHCI
Me
aJ r
Me
o
NHPh
65%
Barluenea.;Aznar, F.; Fraiz, S. Jr.; Pinto, A.C. Tetrahedron LRti., 1991. 32, 3205.
-%
CHO
Ts- N=TSN- Ts
b
PhMe , toluene, 1 h
Trost.;Marrs, C. J. Org. Chem., 1991, 56, 6468. PhNH2, NaBH4, MeOH 3M H2SO4, THF
Verardo, G.;
..
b
; Favret, G.; Strazzolini, P. Synthesis, 1991, 447.
1. I-BuNH~ 2. LDA , THF
\CHO Stevens,
3. CI(CH2)3Br, THF ,0°C 4. iPrONa ,iPrOH
c.;De Kimoe. & SynLett, 1991, 351. Related Methods: Section 102 (Amines from Ketones)
pBU 44%
142
Compendium of Organic d j ?:dietic Methods, Vol8
SECTION 95:
Section 96
AMINES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 96: AMINES FROM AMIDES
-
1. Me3SiC1, NEt3
PhMe ,40°C , 4 h
N H
2. BuLi
Q
B
U 70%
m,Miao, S.W.; Bharathi, S.N.; Katsuhira, T.; Bravo, A.A. J. Org. Chem., 1990, 55,
-
3682.
NaBH4,25"C, 50 h Br-
4bbori.
68%
EtzN-Me
Br
L,Takanohashi, Y . Chem. Lett., 1990, 251. 1. 2.2 eq. PhLi ,THF ,O°C 2. H 2 0 , O°C c
Ph
*3+
r Ph
PhSeSePh 73%
94%
Sekiguchi, M.; Qgawa. A; Fujiwara, S.; Ryu, I.; Kambe, N.;Sonoda. N. Chem. Lett., 1990, 2053.
0
NaBH4, THF ,65OC, 4 h (BrCH2CH212SeBr2
b
Me2NY Me
Me,Ne
Me
82%
Akaban.;Takanohashi, Y . J. Chem Soc.. Perkin Trans. I, 1991.479.
aCF3 1. PCl5 2. MeLi
NHAc
3.
/--
0
m
to) N
N-Li
57%
U
Me Strekowski. L,; Petterson, S.E.; Janda, L.; Wydra, R.L.; Harden, D.B.; Lipowska, M.; Cegla, M.T. J. Org. Chem., 1992, 57, 196.
143
Amines from Amides
Section 96
NaOEt ,DMF EtOH ,reflux
f
t
Bu' N
Bu'
Me C02Et 47%
Bartholomew, D.; Stocks, M.J.Tetrahedron Let?.. 1991, 32, 4795.
Ph. N-AC
NaBH4,I2,7O0C, 3 h
*
Ph. N.Et
Me Me Prasad, A.S.B.; Kanth, J.V.B.; Periasamv. M, Tetrahedron, 1992,48,4623.
74%
no N Ts
1. Dibal ,CH2C12, -78°C 2. PPTS
3. Tic14, Me$%-
Ts
87%
h m a n , J.; Somfai. P, Tetrahedron, 1992, 48, 9537.
Kuroboshi, M.; Hivama. T. Tetrahedron Lett., 1992, 33, 4177.
0
0
Ho
AIBN, xylene reflux, 2 h
OH 67% Hirao. K; Mohri, K.; m m i t s u . 0,; Tabata, M.; Sohma, J. Tetrahedron Lett., 1992, 33, 1459.
R
1. PhLi , TlIF -78°C -+ RT
H ;-
H
HCI 62%
McCarthy, K.E.; Martin, M.G. Tetrahedron Lett., 1992, 33, 5895. Related Methods: Section 105A (Protectionof Amines)
144
Section 97
Compendium of Organic Synthetic Methods, Vo18
SECTION 97: AMINES FROM AMINES
Ph-N'
,-
MeOH ,0.25 M NaOH DCN*,12h
Me
*
H
Ph-N:
Et hv (>280nm) Et 80% Sudha Rani, K.; Bhalerao, U.T. Tetrahedron Lett., 2990, 31, 1199. Bu3SnH, AIBN
p o Sherbum. M.S. Tetrahedron Left., 1990, 31, 1625, 3495. Sherbum, M.S.; Dickinson, J.M.; Goodman, C. J. Chem. SOC., Chem. Commun., 1990, 1065. ;Sherbum, M.S. Terrahedron, 1991, 47,4077.
;;-
Bu3SnHI AIBN PhH ,reflux *
H
(O& I 0
q N r 66%
Rosa, A.M.; Prabhakar. S. ; Lobo, A.M. Tetrahedron Left., 1990, 31, 1881.
M Me0
Me0
e
O
T
Me0
Br
'\ -
_____)
0
51%
OJ
\
OJ
0
Takano. S,; Suzuki, M.; Kijima, A.; Ogasawara, K. Tetrahedron Lett., 1990, 31, 2315.
n ( )N
x
4
1 . 4 BnMgCl ether, R T , 12h 2. KOH , aq. MeOH
L,
Qh
Gottlieb, L.; Mevers. A.1, Tetrahedron Left., 1990, 31, 4723.
H
76%
145
Amines from Amines
Section 97
hv ,MeCN
Ph 15% 65%
Lewis.; Reddy, G.D.TetrahedronLett., 1990, 31, 5293. hv (2280 nm) DCN ,MeCN
M
e
>
o
m
' NH
80%
DCN = 1.4-dicyanonaphthalene Pandey, G.;Sridhar, M.; Bhalerao, U.T. Tetrahedron Letf.,1990, 31, 5373.
"0 Me,N
O
0
Me0
Ph
OMe
Tomioka.:Inoue, I.;
MeLi , PhMe , -78; 20 min
Ph)--N'
Me
H
Q
(70% ee, R)
94%
OMe
Shindo, M.; Koga, K. TefrahedronLeft., 1990, 31, 6681.
DAO = pea seedling diamine oxidase Cragg, J.E.; ~
R
.
B Kgaphola, . ; M.M. Tetrahedron Left., 1990, 31,6907.
O2"0\ N
Me
%Me 0
NaHco3, EtOH heat, 3 h
Eulda. A.A,lnd.J. Chem, 1990, 298, 1017.
77%
Me
Section 97
Compendium of Organic Synthetic Methods, Vol8
146
RuClz(PPh3)3
>or" N,
PhMe ,reflux
H
quant.
Tsuji, Y.;Kotachi, S.; Huh, K-T.; Watanabe..!. Org. Chem., 2990, 55, 580.
1. Ti(OiPr)4, PhCHO , RT
-
2. NaBH3CN. H 2 0 , 2 0 h
70%
Mattson.; Pham, K.M.; Leuck, D.J.; Cowen, K.A. J. Org. Chem., 2990, 55, 2552. 1 . iPrMgBr 2. iPrMgBr
L @$ Ph
) N * '
87%
bh
Katritzkv. A.R,; Rachwal, S.; Wu, J. Can. .I. Chent., 1990, 68, 456. Kauitzkv, A.R,; Latif, M.; Urogdi, L. J. Chem. SOL,Perkin Trans. I, 1990, 667. Katritzkv. A.R,; Noble, G.; Pilarski, B.; Harris, P. Chem. Ber., 1990, 123, 1443.
N.OMe
Ph
A ! Me
NaBH4 - XI4, THF , RT b
KH":
Ph
Y2 Me
95%
(64% ee , S)
Itsuno.;Sakurai, Y.;Shimizu, K.; Ito, K. J. Chem. Soc., Perkin Trans. I, 1990, C0,Me
b
EtO
M~
,80"C 2h
*
Me
2. NaOMe 3. heat, 2 h Walizei, G.H.; Breitmaier. E, Liebigs Ann. Chem., 1990, 605.
H
1. BuLi 2. 1-BuLi 3. BuLi ,TMEDA ,20"C
(EtO)ZCO, -50°C -+ 20°C eN-4.5. HzO
1859.
35%
t
85% Foubelo, F.; GonzPez, R.; Fafianb, F.J.; Yus, M. J. Chem. Soc., Chem. Conimun., 2990, 1521.
;-
147
Amines from Amines
Section 97
Li[Ir(dppe)d. H2 (25 bar) THF , CHzCCLz, 30°C. 1 h
Bn .
N=iMe Ph
stainless steel autoclave
=- BnHN
99% ee)
65%
Brown.;Salunkhe, A.M.; Singaram, B. J. Org. Chem., 1991, 56, 1170.
PhMe ,reflux
c
OSiPh2r-Bu
00
OSiPhpBu
(93
Ito, M.; Maeda, M.;
'
Tetrahedron Lert.. 1992, 33, 3765.
7)
AMINESFROM NITRO COMPOUNDS O N 0 2
NH2NH2.y
O N H 2
EtOH ,reflux
Ban. B.H.; Jang, D.G. Tetrahedron Lett., 1990, 31, 1181.
85%
85%
Section 105
Amines from Miscellaneous
Ph.
AI-NiC12-6 H20-THF t
NO2
10 min Sarmah, P.; Barua. N.C. Tetrahedron Lett., 1990, 31, 4065.
NOp
Q
PdC12, EtOHIAcOH cat. Fe , 3 H2,45 min
*
NO2
161
Ph- NH2
6
90%
80%
NO2
.. Theodondls.; Manfredi, M.C.; Krebs, J.D. Tetrahedron Lett., 1990, 31, 6141.
H
85% Kasi Reddy, C.P.R.Org. Prep. Proceed. Int., 1990, 22, 117.
u,
NaSH4-c~S04,EtOH
*
PhNO,
RT , 10 min Yoo. S,; Lee, S. SynLett, 1990, 419. Pb , AcOH-DMF , R?'
Ph-
NO2
30 min
PhNH,
Ph
. ,
H
94%
-"-OH
94%
@+Z) Sera. A,; Yamauchi, H.; Yamada, 11.; Itoh, K. SynLett, 1990, 477. HC02NH4, Pd-C , THF MeOH , 6 h
*
58%
Kabalka, G.W.; Pace, R.D.; Wadgaonkar, P.P. Synth. Commun., 1990, 20, 2453.
P h 7 NO2
SnCl2,3 eq. PhSH 3 eq.NEt3 ,-PhH
10 min
Ph-+ N-OH
(E) Barua, M.; Komea, P.; Urpi, F.; Vilarrasa, J. Tetrahedron, 1990, 46, 587.
98%
162
Compendium of Organic Synthetic Methods, Vol8
Section 105
1. NHflH2, 16OoC,2 h o
N
o
2
acetone, sealed ampule w 2.MeOH
Abdel-Baky, S.; Zhuang, M.;
0
0
N
H
2
95%
Synth. Commun., 1991, 21, 161. e- , Hg electroddC cathode H2S04, iPrOH ,H 2 0
cy""" 87%
Wessling, M.; Schafer. H.L Chem. Ber., 1991, 124, 2303. N02
1.4 eq. SmIz , THF
THF/MeOH , RT , 3 min
*
2. 10%Na2S203
Me0
Me0
Kende.;Mendoza, J.S. Tetrahedron Lett., 1991, 32, 1699.
oNo2 l.Zn(BH& , DME 5OoC, 1 h
2.Hs
Ranu.; Chakraborty, R. Tetrahedron Lett., 1991, 32, 3579. Ru3(CO)lz-NH(iPr)2
o
p
e c=N
CO , H 2 0 , 15OOC. 2 h H 2 N G G N 20 atm
quant.
Nornura. K. Chem. Lett., 1991, 1679.
Ph-NO2
Moo3 ,NazSeq NaBH4, H20
Ph-NH2
c
96%
Yanada. K,; Yanada, R.; Meguir, H. Tetrahedron Lett., 1992, 33, 1463. 5% PdC12(PPh3h
Ph S ~ C I2 ~eq., co
~
1OOOC
NO2 Akazome, M.; Kondo, T.; Watanabe.
PhNO,
W
P
"
Y, Chem. Lett., 1992, 769.
Fe , NH4C.l. H 2 0
w
75%
H
PhNH2
reflux, 1.5 h Ramadas. K .; Srinivasan, N. Synth. Cornrnun., 1992, 22, 3189.
h
g2%
Protection of Amines
Section 105A
163
REVIEWS:
"Electrophilic Aminations with Oxazuidines" Andreae, S.; Synthesis, 1991, 327.
SECTION 105A: PROTECTION OF AMINES
-
20% Pd(OH)*-C , EtOH Parr shaker, H2 (55 psi)
B n H N e O Bn
OBn
H2N*
19 h Bernotas.;Cube, R.V. Synth. Commun., 1990. 20, 1209.
c""S"
ether, 20°C, 30 min
Keumi. T,; Shimada, M.;Morita, T.; Kitajima, H. Bull. Chem. SOC. J'n., H,N
NH,*HCl
I
Bn
M~-CO,E~
0
A N .H *
Bn
aq. HCHO N-Me morpholine dioxane. toluene
Bn .
1990, 63, 2252.
0 N. Bn
( )
87%
N
MeA C0,Et
aq. HCI , MeOH
sHale, ; J.J.; Bastos, M.; Gibson, F.S. Tetrahedron Lett., 1990, 31, 2109.
0SiSz Me M e
Me' Me
RhCI(PPh3)3 , 14 h PhNHz ,80°C
\
also with aliphatic amines
Bonar-Law. R.P.;
Me, ..Me
OS1:N-Ph TB AF
Me'S iMe
72%
or TFAA ; Dorgan, B.J. Tetrahedron Lett., 1990, 31, 6721, 6725.
BF3aOEtZ , EtSH
C N -Cbz Subhas Bose, D.; -Tetrahedron
ether, 8 h Lett., 1990, 31, 6903.
92%
Section 105A
Compendium of Organic Synthetic Methods, Vol. 8
164
1. HCHO 2. cyclopenfadiene ,NMM
4
1. cat. CuSO4, aq. EtOH ,70°C
84%
2. NazSo3 ,aq. NH4CI co. P.A.; Clark, J.D.J. Org. Chem., 2990, 55, 2271.
0
also for protection of ply-01s
Allainmat, M.; L'Haridon, P.; Toupet, L.; -1lec.
H
PhCHNz , SnC12.2 HzO CHzClz, 5.5 d , RT
D, Synfhesis, 2990, 27.
H
Bn I
&OH 40%
8%
Liotta, L.J.; Ganem,B.sr. J. Chem., 2992, 31, 215.
Ph ' I BoczO, NaHCO3 NH2*HCl EtOH ,RT , 3 h
--
)))>>)>> Einhorn. J,; Einhorn, C.; Luche, J-L. SynLelt, 1992, 37.
C0,Me
BnO?
0 , 10%Pd-C
NHCbz BoCzO, EtOH , RT Baiwa. J.S, Tetrahedron Lett., 1992, 33, 2955.
TSO-N ' Boc
H
1. BuLi
-
Ph\
N- BOC H
BnO/\(
Bu.
99%
C02Me
NHB~C
92%
Boc
N' H
81%
2. B B u ~, -78"C, 1 h Gentt, J-P.; Hajicek, J.; Bischoff, L.; Greck, C. Tetrahedron Let?., 2992, 33, 2677.
Protection of Amines
Section 105A
-r H2N
O N3 J *(
mO'N'CO2H H
N3
2eq.NaHC03,18h aq. dioxane
C02H
165
I
85%
N3
ux. B.; Gerardin, P. Tetrahedron Lett., 1991. 32, 351. 0
Brim JI NHBn
I Z - C ~NH2 H ~ ~
.aq. HCHO *
0 ~ I - C ~ H INS
Bn
0 N
aq. HCI
+
N'
91%
Bn
KnaupA; Hale, J.J.; Bastos, M.; Molina, A.; Chen. K.Y,J. Org. Chem., 1992, 57, 6239. AcCl , NaI
*
0
Ihara, M.; Hirabayashi, A.; Taniguchi, N.;
W
N
. Ac
Heterocycles, 1992, 33, 851.
1. PhCHO 2. BWZO
NH,
3.1N KHS04, NaOH
Prueh.;Birchenough, L.A.; Egbertson, M.S. Synth. Also see Section 82 (Amides from Amines)
Bw-N>NH2 Commun., 1992, 22, 2357.
92%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
8
PREPARATION OF ESTERS
SECTION 106: ESTERS FROM ALKYNES
74%
Ni(COD)2, CO2
100°C
Tsuda.; Morikawa, S.; Hasegawa, N.; &cgu&L
%Me3 J. Org. Chem., 1990, 55, 2978.
SECTION 107: ESTERS FROM ACID DERIVATIVES The following types of reactions are found in this section: 1.
2.
3.
Esters from the reaction of alcohols with carboxylic acids, acid halides and anhydrides. Lactones from hydroxy acids Esters from carbxylic acids and halides, sulfoxides and miscellaneous compounds
n-C15H30C00H -G.;
MejNoBH3, reflux 2 xylene, 9 h
n-C,SH3oC02CH,n-ClSH,o
61%
Reho, A.; Latrofa, A.; €AQ&Synthesis, 1990, 853. t-BuOH , activated A1203
0
15 h
Ph>
Ot-Bu
0
85%
m a w a . K,; Yoshitake, S.; Amiya, T.; 110, K. Synth. Commun., 1990, 20, 2033.
n-C8Hl7Br
dry AcOK ,A1203 microwaves
n-C8H170Ac
92%
Bram, G.; J.OUDV.&; Majdoub, M.; Gutierrez, E.; Ruiz-Iiitzky, E. Tetrahedron, 2990. 46, 5167.
Section 107
Esters from Acids
167
EtOH ,cat. H2S04 , I .5 h
c Ph-l 93% Ph 7 1))1)1) CO2Et COOH Khurana. J.M,; Sahoo, P.K.;Maikap, G.C. Synth. Commun., 1990, 20, 2267.
BuBr , Aliquat 3 3 6 , reflux
EtC02Na
+
EtCO2Bu
95%
Synth. Commun., 1991, 21, 1545.
Vinczer, P.; Novak, L.;
1% aq. H~S04.85Oc 8h
Sueahara. K,;Fujita, T.;Watanabe, S.: Sakamoto, M.;Sugirnoto, K. Synthesis, 2990, 783.
hCo2. 1. Dibal , THF , -78OC
3h
2. “FA, CH2C12
Me
no ZnC12
+ Frenette.
ZnCI2
; Monette, M.: Bernsdn, M.A.; Young,
1991, 56, 3083.
40)
(60 (70
R.N.;Verhoeven, T.R.J.
-b
30) Org. Chem.,
PhSeSePh , CuOTF 2 eq. CaCq ,CH2Cl2
CO2H
30°C
quant.
PhSe
Miyachi, N.; Satoh, H.; Shibasaki. M,J.Chem. Soc., Perkin Trans. I, 1991, 2049.
0
CoC12, ether
PhK C1
c
Ph
Ji
-+-
Ph’$’
OEt
49%
Iabal. J,; Srivastava, R.R.Tetrahedron, 1991, 47,3155.
O 27%
.
EtI CsF ,DMF b PhCOOH PhCO2Et Sato, T.; Orera.; Nozaki, H. J. Org. Chem., 1992, 57, 2166.
94%
168
Compendium of Organic Synthetic Methods, Vol. 8
Me
1.2 eq. PIFA , 3 d
*
Section 108
M e h O Phi"
71%
PIFA = phenyliodonium bis-trifluoroacetate
C&3a!aJd,; Manage, A.C.; Murphy, P.J. Tetrahedron Lett., 1992, 33,965.
PhCH,CO,H
Fe(C10&*9 H2O ,EtOH b
PhCHzCO2Et 93%
;
Kumar, H.; Parmar, A. Synth. Commun., 1992. 22, 1087. BnCl ,NaHC03, TBAB NaI ,MeCN ,8OoC, 8 h
0 2 N ~ o o F 5 n Hu, Y.; Pa. W,; Cui, W.;
98%
Synth. Commun., 1992, 22, 2763. BnBr , BnByNCI, neat
L-
n-CSH,iCOOH
n-C5H11C02Bn
microwave (560W) 10 min Yunchene. Y,;Yulin, J.; Dabin, G . Synth. Commun., 1992, 22, 3109.
72%
Further examples of the reaction RCO2H + R'OH -) RC02R are included in Section 108 (Esters from Alcohols and Phenols) and in Section 30A (Protection of Carboxylic Acids).
SECTION 108: ESTERS FROM ALCOHOLS AND THIOLS
53% Baskaran, S.; Chandrasekaran. S, Tetrahedron Lett., 1990. 31,2775. 1. CO, S ,cat. Se
NEt3 , THF ,60"C
L-
x
autoclave, 1 h Me0 S B ~ 2. cat. S , BnBr 250°C 69% Mizuno. T.; Nishiguchi, I.; Hirashima, T.; Ogawa, A.; Kambe, N.; Sonoda, N. Tetrahedron Lett., 1990, 31, 4773.
Esters from Alcohols
Section 108
d
169
*d
1. EtCqNHNH2 2. Pb(OAc)4
OH
CO2Et
87%
Katritzkv.;-Tetrahedron
Lett., 1990, 31, 6781.
Kita. Y,; Sekihachi. J.; Hayashi, Y.; Da, Y-Z.; Yamamoto, M.; 55, 1108.
86%
Mi, S.
J . Org. Chem., 1990,
Ce(SO&, Si02, EtOAc n-C1 lH23
*
n-C11H23
LOAc 15 min Nishieuchi. T,; Taya, J. J. Chem. SOC.,Perkin Trans 1, 1990, 172.
OH
"x
CO , 0 2 ,PdCl2, THF CuCl2, HCl , RT , 1 am
~e*
OH
poly-L-leucine
O
A1Der. H.; Hamel, N. J. Chem. SOC.,Chem. Commun., 1990, 135
KMn04 - CuSO4*5 H20 CH2C12, H20
O
97%
49%
(61% ee , R)
Go
78% reflux (5 min) - RT (4.5 h) Baskaran, S.; Islam, I.; Vankar, P.S.; Chandrasekaran. S. J. Chem. Soc., Chem. Commun., 1990. 1670. lipase PS-30, DME , RT
AcO"'
OH
+
Berkowitz, D.B.;
=/
AcO"'
OAc
OH
47% (>97%ee) Tetrahedron Lett., 1991, 32, 5491.
OH
47% (?97%ee)
170
Compendium of Organic Synthetic Methods, Vol. 8
1. PhI , Pd(0Ac)z , KOAC, I 0 h BnEt3NBr, iBuCN , 9OoC
2. PCC
Ph
*
Section 108
t;.
66%
0
Mandai.; Hasegawa, S.; Fujimoto, T.; Kawada, M.; Nokami, J.; Tsuji, J. SynLeit, 1990, 85. H
O
TPAP - NMO ,MS
V
OH
CH2Cl2
*
0
TPAP = tetra-n-propylamniumpemthenate
A 0x / - -
76%
Bloch. R.; Brillet, C. SynLett, 1991, 829.
SiMe3 OH
Pseudomonas AK 25%conversion d
SiMe, + FSiMe3 OH OAc \
OAc
23% (80% ee)
63% (4% ee)
Sparks, M A . ; Panek. J.S. Tetrahedron Lett., 1991, 32, 4085. porcine pancretic lipase
ether, BuC02CH2CF3 25"C,48 h
Chone.
OH
t
Me-
41% (97% ee)
38% (98% ee) ; Mar, E.K. Tetrahedron Lett., 1991, 32, 5683.
general preparation of angelate esters Harmann, B.; Kanazawa. A.M.; DeprCs, I-P.; Pd(dba)2-dppbt DME CO (40 a m ) , 190T 48 h
=
El Ali, B.; Alner. H,J. Org. Chem., 1991, 56, 5357.
SnMe3
Terrahedron Lett., 1991, 32, 5077.
o
a
78%
Section 108
Esters from Alcohols
171
modified Mitsunobu - for sterically hindered 2" alcohols Martin. S.F,; Dodge, J.A. Tetrahedron Lett., 1991, 32, 3017.
OH
d
HO
NaH.THF S
c
%AS
4+
A d
u
(83
I)
96%
Yamada, S. J. Org. Chem., 1992, 57, 1591. Yamada. S, Tetrahedron Lett., 1992, 33, 2171.
0 Q l B u M e
OH porcine pancreatic lipase
BuCO~CH~CF~ ether, 16 h * F
53% ee
+ 95%ee
36% conversion
Morgan. B.; Oehlschlager,A.C.; Stokes, T.M. J. Org. Chem., 1992, 57, 3231. 1. BKHO , CHzC12, MS 2. BrZnCHzCOzEt , ether
(OH Ph''A H NHBn
3. satd. NhC1 4.112, 10% Pd-C , EtOH
9 bar
/
H2N
co2J3
A*H
50%
Bu
Andres, C.; Gonziilez, A.; Pedrosa. R,; Perez-Encabo, A. Tetrahedron Lett., 1992, 33,2895.
OH
6
COzMe
+oSiMyt-Bu OMe
86% 3M LiCIO, ,ether * 15 min Grieco. P.A.; Collins, J.L.; Henry, K.J.Jr. Tetrahedron Lett., 1992, 33, 4735. MeC03H, NaBr
40°C, 2 h
c
yo0
92%
Morimoto. T,; Hirano, M.; Hamaguchi, T.; Shimoyama, M.; Zhuang, X. Bull. Chem. SOC.Jpn., 1992, 65. 703.
172
Compendium of Organic Synthetic Methods, Vol. 8
Section 109
b
Pickett.;Van Dort, P.C. Tetrahedron Lett., 1992, 33, 1161
6 t-Bu
1.
4 .o ocr:
0 . .
, CHzC12
0°C 2. mCPBA 3. NaHCO3
98%
t-Bu
Morin-Fox, M.L.; hioton. M.A. Tetrahedron Leti., 1992, 33, 5699. Further examples of the reaction ROH -+ -RCO2R are included in Section 107 (Esters from Acid Derivatives) and in Section 45A (Protection of Alcohols and Phenols).
SECTION 109: ESTERS FROM ALDEHYDES n-C3H7CHO
1.5 BrZ , HzO/CHzC12
Me\( c H 2 h 1 - 0 ~
HMPT - NaHC53
0
Me,
(cH2)8qOy
94%
n-C4H9
A1 Neirabeyeh, M.; Pujol, M.D. Tetrahedron Left., 1990, 31, 2273. 0
)-CHO
€Po-(KF, 18-crown-6,1 dMeCN ,70°C
ii"1( yo 85 %
Olofson.;Dang, V.A.; Morrison, D.S.; DeCusati, D.F. J. Org. Chem., 1990, 55, 1.
CHO
*d
n-C12H250TMS , NBS
AIBN ,95"C, 15 min
Markd, I.E.; Mekhalfia, A.; Qllis. W.D.SynLett, 1990, 347.
On-'lzH25
72%
173
Esters from Amides
Section 111
2.6eq.KOH 1.3 eq. I2 ,MeOH , 1 h
PhCHO
c
98%
PhC02Me
Yamada.; Morizono, D.; Yamamoto, K. Tetrahedron Lett., 1992, 33, 4329.
OAc €lb,,,OEt MeO"' Gbmez, A.M.; ,-
1. NazCO2 ,MeOH 2. TBPSCl , irnidazole
t-BiPh2Si0
*
DMF , 4OoC , 2 4 h 3. rnCPBA , BF3-OEtz CH2C12, -10°C
MeO"'
Lbpez, J.C. Tetrahedron Lett., 1992, 33, 5105. 1. NHzOH-HCI , NaOAc MeOH , reflux, 4 h
PhCO2Me
PhCHo
2. H202,2-NBSeA, MeOH * reflux, 1 h 2-NBSeA = 2-nitrobenzene seleninic acid Said, S.B.; Skarzewski, J.; Mlochowski. J, Synfh. Commun., 1992, 22, 1851.
72%
Related Methods: Section 117 (Esters from Ketones)
SECTION 110:
ESTERS FROM ALKYLS, METHYLENES AND ARYLS
No examples of the reaction R-R -+ RCO2R' or R'C02R (R,R' = alkyl, aryl, etc.) occur in the literature. For the reaction R-H -+ RCO2R or RC02R, see Section 116 (Esters from Hydrides).
NO ADDITIONAL EXAMPLES
SECTION 111: ESTERS FROM AMIDES OMOM SnBu3
1. BuLi , THF , -78°C 2.
= L N 0
Me
'NMq
3. 1.5 eq. conc. HClO4 CHzClz , RT, overnight M .J-;.
Mar, E.K. Tetrahedron Left., 1990, 31, 1981.
43 % (92%ee)
Compendium of Organic SyniirbucMethods, Vol. 8
174
Section 113
SECTION 112: ESTERS FROM AMJNES Ph
Y
CO2H
NH2
VO(OEt)C12 EtOH , 1 h
Ph-COZEt
0
+
PhK C02Et
(89
11)
Hirao, T.; Ohshiro, Y. Tetrahedron Lett., 1990, 31, 3917.
74%
SECTION 113: ESTERS FROM ESTERS Conjugate reductions and conjugate alkylationsof unsaturatedesters are found in Section 74 (Alkyls from Alkenes).
Saha, G.; Bhattacharya, A.; Roy, S.S.; Ghosh. S, Tetrahedron Left., 1990, 31, 1483.
1. H2 (100a m ) , S-BINAP
2.1130+
Me
L o , ,
*
b
Me
96%
(99.5% ee)
Ohkuma, T.; Kitamura, M.; Novori. R. Tetrahedron Lett., 1990, 31, 5509.
using Tic14 gave fused > spirocycle in all cases
K=Me __R = Et
R = Pr
31)
(69 (75 (>1 \
25) 99j
-
Black. T.H,; McDennott, T.S.; Eisenbeis, S.A. Tetrahedron Letf., 1990, 31, 6617.
(C02Me
Bu~N Br(CH2)4Br, BF4, B NMP u~NI
e- ,A1 anode, 0.2 Amp -L
C0,Me O C 0 2 M e 40%
stainless steel cathode Folest, I-C.; Perichon, J. J. Org. Chem., 1990, 55,2503. Lu, Y-W.; NCdelCc. J-Y,;
72% 31% 64%
175
Esters from Esters
Section 113
6
1. LDA , Me3SiCI
2. MeCHCI, , BuLi 3. xylene , reflux, 10 h
4. H, , Pd-C, 4 atm.
11%
Fouque, E.; R o u s s e e; Seyden-Penne, J. J. Org. Chem., 1990, 55,4807. Br
10% T i C 4 , CHzClz * c02et 97% 40°C , 10 min (1:l erythro:threo) 2. 10%aq. HCI J. Chem. Soc., Chem. Commun., 1990, 767. Hayashi, M.; Sugiyama, M.; Toba, T.; 1. EtMgBr 2. EtCHO
C02Me Et (2.3
Kurasawa, Y.;Yokota, K. Chem. Lett., 1990, 719.
;K-.
0 1)
77%
e- , Pt elecuodes , MeCN Ph-OH
-hi.
t
BufiI, RT MA;Tsukamoto, Y.;Minami, T. Chem. Lelt., 1990, 1223.
Citterio. A.; Sebastiano, R.; Nicolini, M.; Santi, R. SynLett, 1990, 42.
other R3AI and R2AICI reagents used Maruoka, K.; Banno, H.; Yamamoto. H.SynLett, 1991, 253.
83%
176
Compendium of Organic Synthetic Methods, Vol. 8
-
Section 113
85% Carfagna, C.; Marian,L.; Musco.;Sallese, G.; &WJL J. Org. Chem., 1991, 56, 3924. BgSnH , AIBN , PhH (0.02 M),reflux
0
OK SePh
92%
Bachi.M.D.;Bosch, E. J. Org. Chem., 1992, 57, 4696. C0,Et
1. 2.2 eq. CH2Br2
2.2 eq. L i m p
2.2 eq. LiHMDS 3 . 4 eq. sec-BuLi 4.2 eq. n-BuLi 5. EtOH , HCI Kowalskl.; Reddy, R.E. J. Org. Chern., 1992, 57, 7194.
C O , M ~ t-BuOK ,THF ,air 24°C P h 4 OMe
-
79%
PhCOzMe
Heckmann, B.; Alayrac, C.; m w s k i . C;Chandrasekhar, S.;
73% Tetrahedron Lett.,
1992, 33, 5205.
Phq
OSiMa '
(
OSiMe3 $@-$F
nOpP
-
Sn(OTf)2, RT , CH2C12
95 %
RT,2h
Mukaiyama, T.; Shiina, I.; Miyashita, M. Chetn. Lett., 1992, 625.
SECTION 114:
n 0 X Me OEt 0
ESTERS FROM ETHERS, EPOXIDES AND THIOETHERS
4zzre!
TiC4, -78°C CH2CIz
-
n
0 Me
0
65 %
C0,Me
Collins, D.J.; Chw, G.L.P.; Ohrist, H. Ausr. J. Chern., 1990, 43, 617.
Section 115
Esters from Halides
177
CO2-02 (65 psi) ,70°C Rh(NBD)@-MezPh)3 BF4
* O Y 3
7d
150 turnovers
J. Chem. SOC.,Chem. Commun., 1992, 1334.
Fazlur-Rahman, A.K.; Tsai, J-C.;
SECTION 115: ESTERS FROM HALIDES AND SULFONATES
1)
(2.6
61%
Gno.;Duann, Y.F. Org. Prep. Proceed. Int., 1990, 22, 85. CICH2C02Me, NiBr2 e- (A1 anode, C cathode)
--
DMF , B u d B r , 2,2-bipy Conan, A.;
; dIncan, E.' Perichon, J. J. Chem.
Co(CO)4, Bu4N1, CO NaOEt , PhH
-
SOC.,Chem. Commun.. 1990, 48.
PhCH2COzEt 95% PhCH2Br Kantam. M.L,; Reddy, N.P.;Choudarv. B.M. Synth. Commun., 1990, 20, 2631.
1
PhMgBr ,THF , 10°C, 2 h .r
0 PhAOMe
OMe Satyanarayama, G.; i S h c a m A Synth. Commun., 1990, 20, 3273. Me0
10% C%(CO)a, NaI CO (50 atm) , TMU
EtOH , l00"C. 24 h
*
Ph
87%
C0,Et 61%
"MU = tetramethyl urea Urata, H.; Goto, D.; Fuchikami, T. Tetrahedron Lett., 1991, 32, 3091.
1
AcOH ,NaOMe ,40°C
autoclave, N2 (15 bar)
PdClAPPh3)Z , 4 h*
aco2M
Carpentier, J-F.; Castanet, Y.: Brocard, J.; Mortreux. A,: Petit. F. Tetrahedron Lett., 1991, 32,
4705.
Compendium of Organic Synthetic Methods, Vol. 8
178
PhOTf
-T
c
OSiMe?
Section 116
[~~-CsH7+'d(OAc)z Me C02Me LiOAc ,dppf, reflux 73% 6h dppf = 1,l'=bis(diphenylphosphino)ferrocene Fiorani, T. J. Org. Chem., 1991, 56, 261. Carfagna, C.; Musco.;Sallese, G.; Santi.;
OSO,F
W O A d z dppp mt3 DMSO , MeOH , CO I
*
60°C. 2 h
(yoZMe*8%
Roth. G.P,; Thomas, J.A. Tetrahedron Lett., 1992, 33, 1959. TBAF.3 H z 0 , Mo(CO)6, THF
I(CH2)41
t
reflux ,20 h
Imbeaux, M.; Web. H.; Moughamir, K.; 1992, 1678.
Rolando.C..Chem. Soc., Chem. Commun.,
1. Bu3SnC=COEt, PdClz(PPh3)z
PhI
EhNCI , DMF
2. H2SO.4,aq. acetone, reflux
PhCH2COZEt
c
Sakamolo, T.;Yasuhara, A.; Kondo, Y.; XamwhJL S y n k n , 1992, 502. Related Methods: Section 25 (Acid Derivatives from Halides).
SECTION 116: ESTERS FROM HYDRIDES
'
This section contains examples of the reaction R-H (R = alkyl, aryl, etc.).
-+ RC02R' or R'C02R
5% Pd(OAch, AcOH 20% benzquinone
2 eq. MnOz ,60°C 50°C Hansson, S.; Heumann. A, ; Rein, T.; hermark, B. J. Org. Chem., 1990, 55, 975.
60%
179
Esters from Ketones
Section 117
5% Pd(OAc),, AcOH 5% Cu(OAc)z, 5OoC
10%hydroquinone
935%
1 am. 0 2 , 2 2 h
Bystrom, S.E.; Larsson, E.M.; hermark, B. J. Org. Chem., 1990, 55, 5674.
Demir. A.S,; Sayrac, T.; Watt, D.S. Synthesis, 1990, 1119. Also via: Section 26 (Acid Derivatives) and Section 41 (Alcohols).
SECTION 117: ESTERS FROM KETONES Pb(OAc)4, BF3oOEtz MeOH , PhH , 12 h
=
Ph
Ph-C02Me 68%
Mathew, F.; My&&&
Tetrahedron Lett., 1990, 31, 3757.
OH Ph
1. Ce ,THF, RT
Br -CO,Et
2. acetophenone
G:e 0
i- P h H M e
70%
Me OH
20% Fukuzawa. S,; Sumimoto, N.; Fujinami, T.; Sakai, S. J. Org. Chem., 1990, 55, 1628. 0-
Ph
pc-0
Me
l.THF, 2. H 2 0
P h s o r 50%
Gong, L.; Leung-Toung, R.; Tidwell. T.T. J. Org. Chem., 1990, 55, 3634.
Bakash. 0.; Goyal, S.; Moriatrv, R.M,; Khosrowshah. J.S. Id.J. Chem., 1990, 298, 304.
Compendium of Organic Synthetic Methods, Vol. 8
180
Acinetobacter calcoaceticus NClB 9871 n-C1 lH23
tetraethyl pyrophosphate
Section 117
0
tl
11H23
25% (74% ee)
+ 65% recovered ketone (36% ee)
Alphand, V.; Archelas, A.;
J. Org. Chem, 1990, 55, 347.
0
;:y;)y
mCPBA ,CHZCIZ,~O"C
SnBu3
n-C6H 13
w
n-C& &02Bn
Me
Me Bakale, R.P.;Scialdone, M.A.; Johnson. C.R, J. Am. Chem. Soc., 1990, 112, 6729.
0 MeOJ
Me0
COZEt
TiC14, MeCN n-C3H7 -45T
2. H 2 0 3. cat. p-TsOH ,PhH (94 6) 68% reflux Saipo.; Shimada, S.; Hashimoto, Y.; Nagashima, T.; Hasegawa, M. Chem Letr., 1990, 1101. 0
"[d Sph , LDA ]
THF , -78°C -+ 0°C
2. mq. NH&I
*
9' 92%
Panheiser. R.L.; Nowick, J.S. J. Org. Chem., 1991, 56, 1176. Acineiobacier NClB 987 1
-
0
BnO+
OH
35% endo (95% ee) 8% ex0 (89% ee) Konigsberger, K.; Alphand, V.;Furstoss, R.;Griengl, H. Tetrahedron Lett., 1991, 32,499. 26% (85% ee)
Section 117
181
Esters from Ketones
oxone . "wet alumina"
/-0
Hirano, M.; Oose, M.; ~ M ~ Q Chem. uLL Lett., 1991, 331. 1% Ni(dpm)2, iRCHO
OL ,WE, RT ,overnight
0
0
67%
Ni(dpm)2 = bis-(dipivaloylmethanato)nickel (11)
Yamada. T,; Takahashi, K.; Kato, K.; Takai, T.; Inoki, S.; Mukaivama. T, Chem. Left., 1991, 641. Na2C04 ,CF3COOH O°C-+RT,2h
x
-
0
0
81%
Olah. G.A.; Wang, Q.; Trivedi, N.J.; Suwa Prakash. G.K. Synthesis, 1991, 739.
-
;iOMe
e - , Et4NOTs , RT
n-CioH21 SiMe,
MeOH
n-ClOH21
Yoshida.; Itoh, M.; Matsunaga, S.; Ime.3. J. Org. Chem., 1992, 57, 4877.
0-
1. DMF (H20) ,NaH 2. EtBr
Delgado, A.;
aTetrahedron Lett., 1992, 33, 2789. cat. Fe@3 ,02, RT PhCHO , PhH
\
*
I ,
b
c02Et
w%
76%
98%
Murahashi. S-IL;Oda,Y.; Naota, T. Tetrahedron Lett., 1992, 33, 7551. cyclohexanone oxygenase (E.C.I.14.13.-) cat. NADP+ ,pH 8 ,glycine-NaOH glucose 6-phosphatdglucose 6-phosphate dehydrogenase
'8
62%
(80%ee)
Taschner.;Peddada, L. J. Chem. Soc., Chem. Commun., 1992, 1384. Also via: Section 27 (Acid Derivatives).
Compendium of Organic Synthetic Methods, Vol8
182
Section 119
SECTION 118: ESTERS FROM NITRILES PPE-Me , MeOH , 150°C, 24 h
*
P h 7 CN
97%
P h 7 C02Me
PPE-Me = plyphosphate methyl ester - see 1. Org. Chem., 1969, 34.2665
Mills. F.D.; Brown, R.T. Synrh. Commun., 1990, 20, 3131.
SECTION 119: ESTERS FROM ALKENES
J. Org. Chem., 1990, 55. 891.
Baskaran, S.; Islam, I.;
.
18 h , O " C + 66°C 2. NaOH H202, 0°C
BzO Hara, S.; Kishimura, K.;
'
e-
BzO
A C02Me 75%
; Dhillon, R.S. J. Org. Chenz., 1990, 55, 6356.
1.2 eq. Phl(0Ts)OH C H S I , , 0°C
,,,,
SiMe3 2. 2.2 eq.imidazole H
H
"
(3
1)
87%
OTs
Schaumann. E.; Kirshning, A. J. Chem. Soc., Perkin Trans. I, 1990, 1481.
Inornata. K.; To&, S.; Kinoshita, H. Chem. Lett., 1990, 1567.
OH
1. Me2SmBH3 ,ether -78°C + 25°C 2. Na2Cr207.2 H 2 0 H2SO4, H2O , 10°C + reflux
Mandal.;Mahajan, S.W. Synthesis, 1991, 311.
40%
Section 120
Esters from Miscellaneous
7 Me
1. Thex-BH2 , THF NaCN, TFAA
Me
NaOOH
OBn 2. mCPBA , CH2C12
+
183
&OBn Me
Me
57%
Yokovama. Y,;Kawashima, H.; Kohno, M.;Ogawa, Y.; Uchida, S. Teiruhedron Len.,2991, 32,1479 2% PdC12(PPh& , TIlF
CGEt
SiMe3 90°C , CO (60 kg/cm2)
+
Bu
EtOH
-.-
Bu
LSiMe3 -I-
C0,Et B
U
(96 with C q ( C O ) *
A
(0
SiMq 70%
4)
loo)
18%
Takeuchi. R,; Ishii, N.; Sam, N. .I. Chem. Soc., Chem. Conimun., 1991, 1247. Also via: Section 44 (Alcohols).
SECTION 120:
ESTERS FROM MISCELLANEOUS COMPOUNDS
10)
(90
Trost. B.M,;Medic, C.A. .I. Org. Cheni., 2990, 55, 1127.
(CO)@=(
OEt Ph
)8 ,acetone ,20°C
611
Ph- C02Et
c
97%
3h
Lluch, A-M.; Jordes, L.; Shnchez-Baeza, F.; Ricart, S . ; Camps, F.; Messepuer. A.; Morel6 J.M, Tetrahedron Leir., 1992, 33, 3021.
Wang, S.L.B.; Su, J.; Wulff. W.D..I. Am. Chem. Soc.. 1992, 114, 10665.
Me,Si
+c=o
H
EtCHO , MABR -78°C , 2 h
Eo
Me3Si * Et
MABR = methyl aluminum bis(4- hromo-2.6-dir-hu tylphenoxide)
Maruoka, K.;Conception, A.B.;
SynLRtt, 1992, 3 1 .
82%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 9 PREPARATION OF ETHERS, EPOXIDES AND THIOETHERS
SECTION 121:
ETHERS, EPOXIDES AND THIOETHERS FROM ALKYNES
Takai.;Tezuka, M.; Kataoka, Y.; U ~ ~ Q & J.J LOrg. Chem., 1990, 55, 5310. SECTION 122:
ETHERS, EPOXIDES AND THIOETHERS FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 123:
ETHERS, EPOXIDES AND THIOETHERS FROM ALCOHOLS AND THIOLS M q S iCHNz 42% aq. HBF4 CH2Cl2, O°C
O -H
a
Ic
-0Me
Aovama.,Shiori, T. Tetrahedron Lett., 1990, 31, 5507. OH
OH
CDCl3 , RT , Tf20
Ph3P=O, 20 min
92%
-0
Hendrickson.;Hussoin, MdS. SynLett, 1990,423.
0
quant.
Section 123
Ethers from Alcohols
mCPBA , MeOH
n-C 13H27
SePh
185
wo
n - ~ , 3 ~ 2 7 L
25°C
97%
Et OH Et Tkmura.; Ohe, K.; Sugita, N. J. Chem. Soc., Perkin Trans. I, 1990, 1697.
H-C3 C-
n
HS n-C4H9
SH
02.
,BPQ, MeOH
* n-c4Hg[s)
PhH
49%
S
Demchuk, D.V.;Lutsenko, A.I.; Troyanskii, E.I.; Nikishin, G.I. Izv. Akud. Nauk. SSSR, 1990. 39, 2801 (Engl.. p. 2542). Ph
=/
$0.15BF3*OEt2
PhH , RT
.-
64%
Ph
0
OH
(9O:lO
ZE)
Inoue, T.; Inoue, S.; WLK, Chem. Lett., 1990, 55.
c7(
Ph4SbOMet DCE , 6 0 T sealed ampule, 24 h Fujiwara, M.; Hitomi, K.;
Synthesis, 1990, 106.
74%
1. e- ,Pt electrodes, MeCN EbB Nr
* Bu-S-BU 86% 2.BuBr Petrosvan.;Niyazymbetov, M.E.; Konyushkin, L.D.; Litvinov, V.P. Synthesis, 1990, 841
BUSH
EtI ,9% TBAB , KOH
OH
neat,6O0C,24h
*
E
t
O
O OEt 90%
Loupy, A.; Sansoulet, J.; Diez-Barra, E.; Carrillo, J.R. Synth. Commun., 1992, 21, 1465. Bu3P-PhSSPh
c-
1 a m ,16 h 90% quant. 10 kbar, 62"C, 3 h Kotsuki., Matsumoto, K.;Nishizawa. H. Tetrahedron Lett., 1991, 32,4155.
Compendium of Organic Synthetic Methods, Vol8
186
TFA , RT , 3 0 min+
OH
Section 124
H *o
OH
Ismail., Hilton. M.J.;
63%
SlefinoviC,M . Tetrahedron Lett., 1992, 33, 3795.
oJoLo9
( Y O H
57%
Synth. Commun., 1992, 22, 687.
Guy, R.K.;
6: eoH , 140°C
2q.
2eq.KzC03,2h
*
5% CUI * )"
(71% ee,R)
OMe
- Mro
Smith.;Jones, D. J. Chem. Soc., Perkin Trans. I, 1992, 407. 1.2 q.(CF3C02)2Hg CH2C12,20aC ,18h
Ph+OH Ph Me
l13:1)
Schultz.;Harrington, R.E.; "ham, F.S. Tetrahedron Lett., 1992, 33, 6097.
SnBq
NPSP , SnC14 ,-78"C CH2C12
NPSP = N-phenylselenophthalimide
Herndon. J.W.; Harp, J.J. Terruhedron Letr., 1992, 33, 6243.
68%
Section 134
Ethers from Alkenes
197
-
Bu3SnCI. NaCNBH3
.
OSiMe,CH,B r AIBN r-BuOH
b
reflux, 8 h
(1
1)
Koreeda.;Visger, D.C. Tetrahedron Lett., 1992, 33, 6603. 25 eq. MeCHO , 0 2 40"C,6h
86%
80%
0
Kaneda. K,; Haruna, S.; Imanaka, T.; Hamamo~o,M.; Nishiyama, Y.; Jshii, Y. Tetrahedron Lett., 1992, 33, 6827. 2.5% Ni(&np)2,02 (1 atm) 2 eq. i W H O , RT
-
b 0
Ni(dmp)z = [ 1,3-bis(pmethoxyphenyl)-1.3-propanedionato]nickel 01)
quant
Yamada. T,; Takai, T.; Rhode, 0.;Mukaiyama, T. Buff. Chenr. Soc. Jpn., 1991. 64, 2109.
Takai.;Hala, E.; Yamada, T.; Mukaiyama, T. Bull. Chem. SOC.Jpn., 2991, 64, 2513 [witli Fe(dmph1. Mukaivama. T,; Takai, T.; Yamada, T.; Rhode, 0. Chetn. Lett., 1990, 1661. Yamada, T.; Takai, T.; Rhode, 0.;Mukaivama. T, Chetn. Lett., 1991, 1. N-methylimidazole , t-BuCHO Mn (salen) derivative PhF, RT ,02
*
& /
78%
(63% ee , lS,2R) Yamada, T.; Imagawa, K.; Nagata, T.; Mukaiyama, T. Chem. Lett., 1992, 2231. Takai, T.; Hata, E.; Yorozu, K.; Mukaiyama, T. Chent. Leit., 1992, 2077.
Mn W e n ) derivative
(34%ee , RR) . SynLett. 1992, 407. Hatayama, A.; Hosoya, N.; Irie, R.; Iio, Y.; ' Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Tetrahedron Lett., 1990, 31, 1345. ' Irie, R.; Noda, K.; Ito, Y.; Tetrahedron Lert., 1991, 32, 1055. ' Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Tetrahedron Asymmetry, 1991, 2, 481.
Section 135
Compendium of Organic Synthetic Methods, Vo18
198
PhIO , Mn porphyrin
c
imidazole
Ph
10
45%
(48% ee) Konishi, K.; Oda, K.; Nishida, K.; Aida, T.; Inoue.. Am. Chem. SOC., 1992, 114, 3 3.
Ph%
2 eq. iPrCHO ,02, DCE
Ph
Ph
b
Ph 2% Ni (salen) derivative, 10 h Oda,T.; Irie, R.; YilfSuki. T,; Okawa, H. SynLet?, 1992, 641. Irie, R.; Ito, Y.;&@&J ’ Tetrahedron Lett., 1991, 32, 6891.
SECTION 135:
88%
ETHERS, EPOXIDES AND THIOETHERS FROM MISCELLANEOUS COMPOUNDS (7:2: 1) NaH:t-AmONa:Ni(OAc)z THF , 16.5 h
0
n-C,2H&” n-CI2H2;
n-C 2H25
n-C l2H;;’*
67%
Becker, S . ; Fort, Y.; Caubkre, P. J. Oig. Chem.. 1990, 55, 6194.
Ph,
QS.
BnBr , 3 eq. DMF , 155°C
*
Me
Bernard, A.M.; Caredda, M.C.;
. .
Bu-
Me
70%
Piras.;Serra, E. Synthesis, 1990. 329.
TiC14, NaI , MeOH , RT 5 min
0
S.
Ph,
Bu
t
92%
s I
Synthesis, 1991, 155.
4 eq. MesSiOMe ,60°C
PhOMe 51%
m. G.A.; Wu, A. Synthesis, 1991, 204. Q
Lawesson’sreagent THF , RT
Bartsch.;Erker, R. Tetrahedron Lett., 1992, 33, 199.
Ph’
s, ph
Ethers from Miscellaneous
Section 135
'-
0 Bu'
Bu
2 eq. TsOH , 2 eq.NaI
30 min
-
/
Bu'
199
*'
Dtabowicz. J,; Dudzinski, B.; Mokdajczk, M. SynLett, 1992, 252. REVIEWS: "Recent Developments in the Area of Annulated Furans" Padwa A,; Murphree. S.S. Org. Prep. Proceed. int., 1991, 23, 547.
Bu
quant.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 10 PREPARATION OF HALIDES AND SULFONATES
SECTION 136:
HALIDES AND SULFONATES FROM ALKYNES NO ADDlTIONAL EXAMPLES
SECTION 137:
HALIDES AND SULFONATES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 138:
HALIDES AND SULFONATES FROM ALCOHOLS AND THIOLS
1 0' 60-98%
IJgge.
G .L,; Gottardo, C. Synrh. Commun., 1990, 20, 1473.
0""
CFCI, , -78°C -+ 20°C
Olah. G.A,; Li, X-Y.SynLert, 1990, 267.
67%
Section 138
20 1
Halides from Aldehydes
Bay, E.; Bak,D.A.; Tmony, P.E.; Leone-Bav. 4 . J . Org. Chem., 1990, 55, 3415. P2I4 , l o 2 ~ O K,85"C
*
OH
-1
86%
Lame. M-Q; Cairon, P.; Villemin, D. Synth. Commun., 1990, 20, 41.
Ph
OTHP
LiBroBF3 ,ether
ph&Br
'53%
also with NabBF3 to give iodides and with 1" and 2" OTHP derivatives Vankar.;Shah, K. Tetrahedron Lett., 1991, 32, 1081. (BrCHzCH2)2SeBrz ,80"C b n-CBHl7OH 7h n-C8H17Br Bkabori.; Takanohashi, Y. Bull. Chem. SOC. Jpn., 1991. 64, 3482.
0
98%
0
3 q.M@N=CC12 C1 dioxane ,40"C , !XI min
HO-&OH OH OH
*
a&c1OH
OH
73%
Benazza, M.; Uzan, R.; Beaupere, D.; Demailly, G. Tetrahedron Lett., 1992, 33, 3129, 4901.
-OH n-CsH11
Ph3P.Brz. MeCN Py , 0°C - RT
&Br 96%
n-C5H11
Sandri, J.; Viala. J, Synth. Commun., 1992, 22, 2945.
SECTION 139:
n-C,H13CHO
HALIDES AND SULFONATES FROM ALDEHYDES "(PhO)3PBrz" , CH2C12 -15°C 3 0°C
Hoffmann. R.W.; Bovicelli, P. Synthesis, 1990, 657.
>
n-C,H,,-(
Br Br
70%
Compendium of Organic Synthetic Methods, ~ 0 1 8
202
Section 142
1.Tf20
-CHO
2. Buq' PhjSnF2-
* 4F
68% Martinez. A.G.; Barcina, J.O.; Rys, A.Z.; Subramanian, L.R. Tetrahedron Lett., 1992, 33, 7787.
SECTION 140:
HALIDES AND SULFONATES FROM ALKYLS, METHYLENES AND ARYLS
For the conversion R-H --t R-Halogen, see Section 146 (Halides from Hydrides). NO ADDITIONAL EXAMPLES
SECTION 141: HALIDES AND SULFONATES FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 142: HALIDES AND SULFONATES FROM AMINES
F
quant.
Kim. Y.H,; Lee, C.H.; Chang, K.Y. Tetrahedron Left., 1990, 31, 3019.
RT + reflux 2.MeCN,
CN-H /
70%
Smith. W.B,; Ho, 0-C. J. Org. Chem., 1990, 55, 2543.
0 Bu
2. PhSH 3.6 eq. AgNO3, PhMe' HF-PV . 90°C I
,
+ Bu
Q BU
54% 39% Haroulounian, S.A.; Di Zio, J.P.; Katzenellenbogen, J.A. J. Org. Chem., 1991, 56, 4993.
Halides from Halides
Section 144
NBS , Py/(HF),
N-NH,
PhL
203
*
Ph
m; Reddy, V.P.; Li, X-Y.; Cm&& Synkrt, 1990, 594.
0
NH,
0''
Me3SiCl , NaNO2 BnEgNCI , CCI4
*
10h
86%
Lee. J.G.; Cha, H.T. Terruhedrun Letf., 1992, 33, 3167.
SECTION 143: HALIDES AND SULFONATES FROM ESTERS 4 eq. DBH B u ~ N 'H2F3-
-
63%
DBH = 1,3-dibromo-5,5-dimethyl hydantoin
Kuroboshi, M.;
SECTION 144:
Chem. Lett., 1992, 827.
HALIDES AND SULFONATES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES
-
SECTION 145:
HALIDES AND SULFONATES FROM HALIDES AND SULFONATES H I , 130°C, 5 h
Br
-1
Namavari, M.; Satyamurthy, N.; Phelps, M.E.; E3g&J&
BrMg--Q-Me
+ nN
' 8F
o
90%
Tetrahedron Letr., 1990, 31, 4973.
freon ,O°C
*
8
F
G Me
Satvamurthv. N.; Bida, G.T.; Phelps, M.E.; Barrio, J.R. J. Org. Chem., 1990, 55, 3373.
30%
Compendium of Organic Synthetic Methods, Vo18
204
Q
1. Mg , ether 2. cs2
*
3. XeF2, CH2C12 0°C -+ RT (72 h)
Me
4
Section 145
+
Me
Me
73%
21%
Zupan, M.; Bregar, Z. Tetrahedron Lett., 1990, 31, 3357. 1. Mg
Me
2. cmzrc12
B
h Me B r
r
3.Br2
+
' Br+Br
Me +
Br+Br
Me
Me
(99
1)
Takahashi, T,; Fujimori, T.; Seki, T.; Saburi, M.; Uchida, Y.; Rousset, C.J.; Negishi. E, J. Chem. Soc., Chem. Commun., 1990, 182. MgI2, CS2,48"C, 5 h
75%
=-
>>>>)>>>
TfO
Martinez.;War, E.T.; L6pez, J.C.; Alonso, J.M.; Hanack.; Subramanian, L.R. Synthesis, 1991, 353.
Mcoel CF3SiEt3, KF CuI , DMF/NMP 80"C, 24 h
Urata, H.;
.
.
82%
Tetrahedron Lett., 1991, 32, 91.
0
Br
NaOCl (pH 9) , CHC13 6% Ni TPP , BnBu3NBr --
pJcl
qumt.
TPP = 5,10,15,20-telraphenyl porphyrin OConnor, K.J.; BUKOWS.C.LJ. Org. Chem., 1991, 56, 1344.
Br
CCF2C02Me, KF & I , 120"c, 8 h
c
Ph ph lcF3 84% Su, D-B.; Duan,J-X.; Chen. 0-Y,Tetrahedron Lett., 1991, 32, 7689.
Section 146
Halides from Hydrides
pG"2g f
KF , TMSO2,18O0C 5h
205
F O N O 2 83%
CH
@PPh,
Yoshida, Y.;
@
; Tomoi, M. Chem. Leu., 1990, 769.
CF3Br. Bu4NBr, RT e- , DMF , TMEDA
3bar
Me0
Me0
Paratian, J.M.; Sibille, S . ; Pkrichon, 3. J. Chem. SOC.,Chem. Commun., 1992, 53.
0
Bu4PF-(HF) , MeCN
c
c1
80°C. 12 h Uchibori, Y.; IJmeno, M.; Seto, H.; Qian, Z.;
SECTION 146:
SynLerr. 1992, 345.
(yl+ 0""
HALIDES AND SULFONATES FROM HYDRIDES
0
Ni (salen)
2h
57% Querci, C.; Suologo, S.; Picci. M, Tetrahedron Left., 1990, 31, 6577.
5%
I,,CAN.Ih MeCN
*co$o
AcO
AcO OAc
Asakura. J,; Robins, M.J. J. Org. Chem., 1990, 55, 4928.
AcO OAC
Meoa BnMe3NBr, RT CH2CI2 - MeOH 2h
Kaiirraeshi. S,; Moriwaki, M.; Tanaka, T.; Fujisaki, S.; Kakinami, T.; Okamoto, T. J. Chem. Soc., Perkin Trans. I, 1990, 897.
206
Compendium of Organic Synthetic Methods, Vol8
6
Section 146
HCl-mCPBA , DMF RT ,20 min
Cl
30%
CI
68%
2%
Chung, K.H.; Kim, H.J.; Kim, H.R.; U Synih. Commun., 1990. 20, 2991 12. Ag2SO4, EtOH RT , 15 min
84%
S v . , S y n t h . Commun., 1992, 22, 3215.
m w Lodge, w -; . B.A.; By, A.W. Synth. Commun., 1990, 877.
6 0
. .
CuBr , TFA , MeCN EbNOTs , e-
0
C electrodes, 20 F h o l*
80%
Mllanl.~.; Kobayashi, T.; Koyama, K..I. Chem. SOC.,Chem. Commun., 1991, 1418.
75% Kodomari. M.; Ammokura, N.; Takeuchi, K.; Yoshitomi, S . Bull. Cfiem. SOC.Jpn., 1992, 65, 306.
eoH
Amberlyst-A26*Br3,24 h CH2C12 (dark)
=-
B
r
o
o
H
+
QOH Br
86% 7% Smilh. K,; James, D.M.; Matlhews, I.; Bye, M.R. J. Chem. Soc., Perkin Trans. I, 1992, 1877. IPy2BF4,2 HBF4 c r r 2 c i 2 , RT
+
0' 48%
Barluenga.;GonzBlez, J.M.; Garcfa-Martfn,M.A.; Campos, P.J.; Asensio, G. 1. Chem. Soc., Chem. Commun., 1992, 1016.
Section 147
Halides from Ketones
207
I
5% PhI(0H)OTs ,NIS
MeOH , RT , 2 3 h
84%conversion
Bovonsombat, P.; Angara, G.J.; McNelis. E, SynLett, 1992, 131. a-Halogenations of aldehydes, ketones and acids are found in Sections 338 (HalideAldehyde), 369 (Halide-Ketone), 359 (Halide-Esters) and 319 (Halide-Acids).
SECTION 147:
HALIDES AND SULFONATES FROM KETONES
8
MeNbCI4, ether -78"C-rRT*
67%
also with MezNbCl3
also with aldehydes
Kauffmann. T,; Abel, T.; Neiteler, G.; Schreer, M. Tetrahedron Lett., 1990, 31, 493.
Motherwell.;Wilkinson, J.A. SynLett, 1991, 191. e- , NEt3.3 €IF, DME Yoshiyama, T.;
.
.
F
Phx
Chem. Lett., 1992, 1995.
F
Ph
44%
SECTION 148: HALIDES AND SULFONATES FROM NITRILES NO ADDITIONAL EXAMPLES
SECTION 149:
HALIDES AND SULFONATES FROM ALKENES
For halocyclopropanations, see Section 74E (Alkyls from Alkenes).
h a new HI surrogate
[PhNEtz*BI3], AcOH 10°C + 25°C
--
Reddy, Ch.K.; Periasamv. M. Tetrahedron Lett., 1990, 31, 1919.
82%
I
208
Compendium of Organic Synthetic Methods, Vo18
ph%$?GBr2 @
Section 149
A3,4
70% 20%
A4.'
5%
0
Collado, I.G.; Madero, J.G.; Massanet. G.M.; Luis, F.R. Tetrahedron Lett., 1990, 31, 563.
Kaiieaeshi.;Moriwaki, M.;Fujisaki, S.; Kakinami, T.; Okamoto, T. Bull. Chem. SOC.Jpn., 1990, 63, 3033.
HBr ,20 min 11% 83% HBr ,Si@, 0.7 h 96% 0% (COBrlz. A1~03,20min 99% 0% KrODD.;Daus, K.A.; Crawford, S.D.; Tubergen, M.W.; Kepler, K.D.; Craig, S.L.; Wilson, V.P. J. Am. Chem. SOC.. 1990, 112, 7433.
MnOz, Me3SiC1 , THF
\r\l\/\\
30"C, 6h 84%
Bellesia, F.; Ghelfi, F.; Pagnoni, U.M.; Pinetti, A. Synth. Cummun., 1991, 21, 489. B u ~ N B ~ *CHC13 B~~,
Ph&
P h T p h Br
Ph
700 min 78% r min 98% Berthelot. J.; Benammar, Y . ; Lange, C. Tetrahedron ten., 1991, 32, 4135.
)))>)I)
Ph
CC14 , L E E , Cu(iPrNH2)2CI 72°C. microwaves (600 W)
&
c1 Ph+CCI,
Adamek, F.; HAiek. M, Tetrahedron Lett., 1992, 33, 2039.
90% conversion
Section 150
SECTION 150:
Halides from Miscellaneous
HALIDES AND SULFONATES FROM MISCELLANEOUS COMPOUNDS NO ADDITIONAL EXAMPLES
209
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 11 PREPARATION OF
HYDRIDES
This chapter lists hydrogenolysisand 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 EXAMPLES
SECTION 152: HYDRIDES FROM ACID DERIVATIVES This section lists examples of decarboxylations (RC02H + R-H) and related reactions.
Delbecq, P.; Celerier, J-P.;I&m.nw&
Tetrahedron Lett., 1990, 31,4873.
(Me3Si)3SiH1AIBN PhMe ,80"C, 10 h
Ballestri, M.;
..
0
92%
; Cardi, N.; Sornmazzi, A. Tetrahedron Lett., 1992, 33, 1787.
SECTION 153: HYDRIDES FROM ALCOHOLS AND THIOLS This section lists examples of the hydrogenolysis of alcohols and phenols (ROH
-OH
5.5%P-cyclodextrin 0.4 N KOH , KCNKCI CoCI2.6 H20
Lee, J-T.; Alper. H, Tetrahedron Leu., 1990, 31, 4101.
t
91%
-+
R-H).
Section 153
211
Hydrides from Alcohols
PhyOH
6 Li", 10%DBB 48 h
c
))")
Ph
Ph
'I
72%
Ph
DBB = 4,4'-di-t-butylbiphenyl Karaman, R.; Kohlman. D.T.; Tetrahedron Lett., 1990, 31, 6155.
v
WC12(PMePh2)4 c
99% ee , R)
Tetrahedron Lett., 1992, 33,6331.
87%
213
Hydrides from Esters
Section 158
SECTION 155:
HYDRIDES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 156: HYDRIDES FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 157: HYDRIDES FROM AMINES This section lists examples of the conversion RNH2 (or R2NH)
+
R-I{.
Leone, C.L.; Chamberlin. A,R, Tetrahedron Lett., 1991, 32, 1691. 1. KOH 2.2 eq. NHzCl
NHTs
*
MeO-
56%
Guziec. F.S. Jr.; Wei, D. J. Org. Chem., 1992, 57, 3772.
Ph
y Ph N.
OH
HC02NH4, Pd-C , MeOH RT,2h
Ph-Ph
c
98%
Balicki. R. Gau. Chim. Ital., 1992, 122, 133.
SECTION 158: HYDRIDES FROM ESTERS This section lists examples of the reactions RC02R'
3
R-H and R02CR'
Barton., Jang, D.O.; Jaszberenyi, J.C. Tetrahedron Lea., 1990, 31, 4681.
-+ N-I.
Compendium of Organic Synthetic Methods, Vo18
214
*kSMe
Section 158
2% I - C ~ ~ H ~ S S H 2% dicumyl peroxide Et3SiH
*/\/\/\/
S
92%
Kirwan, J.N.; Roberts. B.P.; Willis, C.R. Terrahedron Leu., 1990, 31, 5093.
A N 0 2
PK" Eo,Et OBannon, P.E.;
1.1MNaOH .EtOH RT 2.DMSOH20 reflux. 30 min
A N 0 2
Ph'" H
+ ph.*-'&*
NO2
11%
79%
J. Org. Chem.. 1990, 55, 353.
-J.&
RhCl(PPh& ,Et3SiH
p@/Me
0 PhH ,reflux Liu. H-J,; Zhu, B-Y.Synth. Conimun., 1990, 20, 557. Ph
SMe
90%
PhSiH3, AIBN , I h PhMe , reflux quant.
U
Barton.; Jang, D.O.; Jaszberenyi, J.Cs. SynLett, 1991.435. 1. MeLi ,ether
2.
xcenE 0°C --t RT
*
- 100°C -+ RT
&Ph
82%
(82%ee , R)
Matsumoto, K.; LluaJL Tetrahedron Lett., 1991, 32,4129.
SECTION 159:
HYDRIDES FROM ETHERS, EPOXIDES AND THKOETHERS
This section lists examples of the reaction R-0-R' + R-H.
MeOy
0~~ 1. Et3SiH, SnBr2-AcBr
Me
CHzCI2 , 0°C
2. Bu3SnH, AIBN PhH , reflux
Onvama.;Ichimura, Y.; Koga, G. Bull.
I
/
/
Chem. Soc. Jpn., 2991, 64, 2581.
85%
Section 160
Hydrides from Halides
215
REVIEWS:
"Transition Metal Mediated C-S Bond Cleavage Reactions" Synthesis, 1990, 89.
Lub. T-Y.; Ni, 2-J.
SECTION 160:
HYDRIDES FROM HALIDES AND SULFONATES
8"
This section lists the reductions of halides and sulfonates, R-X
6
[MeOCH2CH20(CH2)313SnH 5% aq. NaHCO3 , RT ,40 min + hv (sunlamp)
C02H
+ R-H.
88%
Br
a water soluble tin hydride reagent Light, J.; J~E&JYA Tetrahedron Lett., 1990, 31, 2957.
bp
5% Pd(OAc)z, DMF dppp $9O"C,3.5 h
o,
93%
Cabri.;De Bemardinis, S.; Francalanci, F.; Panco, S . ; $anti. R.J. Org. Chem., 1990, 55, 350.
NEt3,10% PdC H2 (65 psi) ,MeOH
Me0
OMe 0S 02CF,
6h
+
Me0
OMe
90% Sail, J.M.; Dopico. M.; Martorell, G.; Garcia-Raso, A, J. Org. Chem.. 1990, 55, 991. NaI ,H3PO4, MeCN reflux, 4.5h
Mandal. A& ; Nijasure, A.M. SynLett, 1990, 554.
Br
e- , 10%SmC13, DMF Bu~NBF~
*
6
0
Hebri, H.; Dubach, E.; Wrichon, J. Synth. Commun., 1991, 21, 2377.
87%
quant.
-
216
Compendium of Organic Synthetic Methods, Vol8
C1
Section 160
E13Si. hexane ,reflux
5% TBHN 2% r-dodecanethiol
96%
TBHN = di-1-butyl hyponitrite
Cole, S.J.; Kirwan, J.N.; 103.
RobeE!s.;Willis, C.R. J. Chetn. Soc., Perkin Truns. I,
(>25
1)
1991,
84%
no Lewis acid (1 >25) 90% .. Guindon. Y ,; Lavallk, J-F.; Llinas-Brunet, M.; Homer, G.; Rancourt, J. .I. Am. Chetn. SOC., 1991, 113, 9701.
1. AII3, MeCN , 80°C, 1 h 2. H 2 0 -
-
Ph
0 A Ph
92%
Borah, H.N.; Boruah, R.C.; Sandhu, J.S. .I. Cheni. Soc., Chem. Commun., 1991, 154. (MesSi)$iMeSH , 80°C t-BUONNOt-Bu , 1 h F
Br
92%
Daroszewski, J.; Lusztvk.;Degueil, M.; Navarro, C.; Conzmun., 1991, 586.
J. Chetii. Soc., Chew
-
NiBrz(dppp) , PPh3 , Zn DMF , MeOH , KI M e 2O"C, 16 h Sasaki.; Sakai, M.; Sakaibara, Y.; Takagi, K. Cheni. Lett., 1991, 2017.
,,hq
Bu3SnH, AIBN
C02Et PhMe , -78°C
~e
Br
hv (sunlamp)
30min
-
OMe Ph k
c 0 2 E t
Me (32
+
9
97%
OMe ph0kfC02Et Me 1)
90%
Guindon.;LavalltSe. J-F.; Boisvert, L.; Chabot, C.; Delorme, D.; Yoakim, C.; Hall, D.; Lemieux, R.; Simoneau, B. Tetrahedron Lett., 1991, 32, 27.
Guindon.;Yoakim, C.; Lemieux, R.; Boisvert, L.; Delorme, D.; Lett., 1990, 31, 2845.
- Tetrahedron
Section 160
Hydrides from Halides
I , 2 , PhMe, 24 h
n-C 1 1 H23
Br -/
lOO"C, 10 eq. NaBG4
I =
Ballesui, M.; 1991, 56, 678.
-
n-CloH21
Ph
64%
SnClzPh
Org. Chem., 1991, 56, 490.
(Me3Si)3SiH
6 ..
11H23
H3C
03
Ph
Blanton.,Salley, J.M.J.
217
#
ArBN 90°C ' PhMec
82%
; Clark, K.B.; Griller, D.; Giese, B.; Kopping, B. J. Org. Chem.,
, ,
Bu3SnH , Pd(PPh3)4
I
25°C. 3 h Taniguchi, M.; Takeyama, Y.; Fugami, K.; Qshima. 1991, 64, 2593.
0' u;
n-C10H21
b
\=
92%
K,;Ytimoto. K, Bull. Chem. SOC..lpn.,
NiBr2, Zn ,EtOH 60°C,20h
Lee, M-S.; Yamaguchi, K.; Kawai, Y.; Sasaki, K.; Sakakibara, Y. Bull. Chem. SOC. Jpn., 1992, 65, 1739.
Ollivier, J.; Piras, P.P.; Stolle, A.; Aufranc, P.;
;
Tetrahedron Lett.,
1992, 33, 3307.
Ph3PH1, MeCN , RT
Ph
3h
4
Kamiya, N.; Tanmatu, H.; Ishii. Y, Chem. Lett., 1992, 293.
Ph
85%
Compendium of Organic Synthetic Methods, Vol8
218
Section 162
REVIEWS :
"New Mechanistic Insight into Reductions of Halides and Radicals with Samarium (11) Iodide" SynLelt, 1992, 943.
Curran.;Fevig, T.L.; Jasperse, C.P.; Totleben, M.J.
SECTION 161: HYDRIDES FROM HYDRIDES NO ADDITIONAL EXAMPLES
SECTION 162: HYDRIDES FROM KETONES
+ R2C-H.
This section lists examples of the reaction R2C-(C=O)R 1. TsNHNHz ,MeOH 2. LiAlH4, THF ,60°C
ph& . . Balllnl.; Petrini, M.;
- Ph-
NO2
66%
J. Org. Chem., 1990, 55, 5159.
P(OiPr)3 , reflux
*
Ph
p
h
w
51%
C)lah.;Wu, A. SynLett, 1990, 54.
1. Dibal , heptane 90°C, 6 h
P h T
Ph
2.2eq.AlBr3,9O0C 20 h Eisch.;Liu, Z-R.; Boleslawski, M.P. J. Org. Chem., 1992, 57, 2143.
Ph
x SEt
Ph
SEt
PzI4 CHzC1z725"C 2h
w
Ph Ph> (85
Saimoto, H.; Kanzaki, A.; Miyazaki, K.; Sashiwa, H.; 1992, 65, 2842.
0 PhA Ph
Et3SiH , PPHF , 0°C + RT -
PhbPh
PPHF = pyridinium poly(hydrogen fluoride)
Olah.;Wang, Q.; Surva Prakash. G.K. SynLett, 1992, 647.
+
65%
Ph Ph+o 15) 85% Bull. Chem. SOC. Jpn.,
96%
Section 165
219
Hydrides from Miscellaneous
SECTION 163: HYDRIDES FROM NITRILES This section lists examples of the reaction, R-C=N isonitriles ( R - N e ) .
-+
3 eq.Btb, THF, 3 h
(-$
R-H (includes reactions of
TN
CN Ph
cN7ph
71%
b r a . K,;Shimamura, Y.;Fujita, M. J. Org. Chem., 1991, 56, 2920. 1. Bu3SnH. AIBN PhH , reflux b
81%
2. DBU
SynLen, 1991, 107. 1. MeLi 2. H2O
P h 3 N
c
Ph?
79%
"normal" nitrile addition with RMgX
KulD.; Romanelli, A.Org. Prep. Proceed. In(., 1992, 24, 7. SECTION 164: HYDRIDES FROM ALKENES NO ADDITIONAL EXAMPLES
SECTION 165: HYDRIDES FROM MISCELLANEOUS COMPOUNDS NaHTe , DMF , RT
PhJ
SOZPh
*
0
P
h 0
p
64%
Huang, X.; Pi, J-H. Synrh. Cornniun., 1990, 20, 2297. S02Ph
S d z , THF , HMPA -2OOC. 30 min
14%
Kiinzer, H.; Stahnke, M.; Sauer, G.; Wiechert, R. Tetrahedron Lea., 2991, 32, 1949.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
12
PREPARATION OF KETONES
SECTION 166: KETONES FROM ALKYNES
0 J. Chem. SOC., Chem. Commun., 1990, 1469.
Subramanian, R.S.;
HCOzH, lOO"C, 6 h
Menashe, N.; Reshef, D.; Sbvo.
&: C-Me
0
92%
Y. J. Org. Chem., 1991, 56, 2912.
NaAuClO4, aq. MeOH
n-C,H,
* -
Sh
0
* n-C,H,%Me
0 60)
(40
Fukuda, Y.; Utimoto. K, J. Org. Chem., Z991, 56, 3729.
94%
PhSeSePh , MeOH , 1 h
Ph- Ci C-H
(NH4)2S208, reflux
P h q o M e 75% OMe Tiecco. M,; Testafem, L.; Tingoli, M.; Chianelli, D.; Bartoli, D. J. Org. Chem., 1991, 56, 4529. *
SECTION 167: KETONES FROM ACID DERIVATIVES 0
n-C91-11$L- c1
0
Me3TI
n-cgH~$LMe
Markb, I.E.; Southern, J.M. J. Org. Chem., 1990, 55, 3368.
85%
Section 167
22 1
Ketones from Acids
Ph
[2 C~(N03)2/H202/2H201
Ph Y Co2H Ph
m
MeCN
Po
Ph
55%
Capdevielle, P.; Maumy, M. Tetrahedron LRtt., 1990, 31, 3891. 1. Me3SiC1, Li/THF 2. air
q;
3. BzCl , AIC13 4. KFDMF
Bennetau, B.; Krempp, M.; Dunogues, J.; Ratton, S. Tetrahedron Lett., 1990, 31, 6179. Nation-H reflux, 30,min PhH 90%
0
0
Yamato.; Hideshima, C.; S u v a Prakash, G.K.; Olah, G.A. J. Org. Chem., 1991, 56, 3955. /L S n B q
Ph-"
0
,EbNC1
0
Ph?
c
0
BusSbCHzPh, THF
PllJ-C,
-78°C + R T , 1 h
c
82%
0
BuzSnClz , 3 0 min Yano,K.;Baba.;Matsuda, H. Chem. Lett., 1991, 1181.
Ph
Ph
87%
Zhang,L-J.; Huang. Y-Z.;Jiang, H-X.; Duan-Mu, J.; Liao, Y. J. Org. Chem., 1992, 57, 774.
Ac1
n-C7H15
3% MnClqLi~,THF BuMgCl , 100°C
1
w
n-C7H15
BU
87%
Cahiez.;Laboue, B. Tetrahedron Lett., 1992, 33, 4439. Cahiez.;Chavant, P-Y.; Metais, E. Telrahedron Lett., 1992, 33, 5245. SnMe3
A
Me&
AIC13, CH2C12 -78°C. 1 h Karin.;Lee, J.C.; SunU, J. Tetrahedron Lett., 1992, 33, 4953. SiMe3
85%
222
Compendium of Organic Synthetic Methods, Vo18
Kc1
Boivin, J.; El Kaim,L.; ZulJ&
-
PhCOOH
1
TFAA , Py ,ether
n-C ISH3 1
1.
Section 168
n-C1SH31 CF3
2ooc ' O'
81%
Tetrahedron Lett., 1992, 33, 1285.
ph3p d C02r-B
Me;?N-
,DMAP
N=C=N-Et
CH2C12 - -
2. oxone 0 79% Yasserman. H.H,; Ennis, D.S.; Blum, C.A.; Rotello, V.M. Tetrahedron Lett., 1992, 33, 6003. 1. cu* 2. BzCl
c1
c-
d
0 p h
65%
Cu* = activated zerovalent copper Stack, D.E.; Dawson, B.T.; J. Am. Chem. SOC.,1992, 114, 5110.
SECTION 168: KETONES FROM ALCOHOLS AND THIOLS
OH
1. MsCl, CHzCI;! NEt3,O"C , 3 h
2. 2 eq. NaOEt ,EtOH 12b ,2S°C a Gmb-like reaction Pestchanker.;Giordano, O.S. Tetrahedron Lett., 1990, 31, 463. u*'
OH
Cr-PILC/I'BHP CH2Cl2, RT ,24 h
LOH 94%
Cr-PILC = chromia-pillaredmontmorillonite
0"
(Shoudarv.; Durgaprasad, A.; Valli, V.L.K. Tetrahedron Lett., 1990, 31, 5785.
WMnOd2
-
-
55%
Firouzabadi. H.; Seddighi, M.; Mottaghinejad, E.; Boloufchian, M. Tetrahedron,1990, 46,6869.
223
Ketones from Alcohols
Section 168
DAIB = (diacetoxyiodo)benzene
Rama Kri-.
30% K.VJ Sujatha, K.;&nil. R.S, Tetrahedron Let?., 1990, 31, 1351.
PhI(02CCF3)2 aq. MeCN , 2 h 0°C
Barret.;Daudon, M. Tetrahedron Left., 1990, 31,4871.
0
73%
0'
Me0
0""
Clz , CH2C12 , Na2CO3 PhCl , RT , 1 h Bull. Chem. SOC.Jpn., 1990, 63, 947. Yamaguchi, M.; Takata, T.; 5% (Ph3SiO)zCrOz, RT
OSiMe3 4 eq. 70% 1-BuOOH
;s
CHzC12
Muzart.; Ajjou, A.N. SynLert, 1991, 497.
4
OH
Me
Hirano, M.; Oose, M.;
Y OH
63%
-
97%
Q0
oxone, CHzClz "wetA1203"
80%
25"C, 2 h
Me
Bull. Chem. SOC.Jpn., 1991, 64, 1046.
CrO3 , "wetAl2O3" , 15 h
*
hexane 0 H h o , M.; Nagasawa, S.; Jvlorimoto. T, Bull. Chem. SOC.Jpn., 1991, 64, 2857.
95%
224
Compendium of Organic Synthetic Methods, Vo18
>:
4
Section 168
,TFP
CHzClz,20min * -20°C Metlo, R.; Cassidei, L.; Fiorentino, M.; Fusco, C.; Hummer, W.; JHger, V.; Chem. Soc., 1991, 113, 2205.
a J. Am.
NMO , CHzClZ MS 4A. TPAP
HO
0
P A P = tetra-n-butylammoniumpermthenate
Miranda Moreno, M.J.S.; S&M&&L;
75430%
Camps Neves, A.S. Tetrahedron Lett., 1991, 32, 3201.
also - aldehydes from R-CH20TMS Piva.0.; Amougay, A.; Pete, J-P.Tetrahedron Letf., 1991, 32, 3993. 9
io+n-C,F7
-fOH
7
n-C4F; F t CFCI,, 0°C RT , 9 h DesMarteau, D.D.; Petrov, V.A.; Montanari, V.;Pregnolato, M.;&a&&. 1992, 33, 7245. PdC12(PPhj)2, DME Ti(OiPr)4 ,Zn(acac)Z
OH
120°C. 18 h
Itoh, K.; Hamaguchi, N.;
98%
Tetrahedron Lett.,
ph51%
; Nomura, M. J. Chem. Soc., Perkin Trans. I, 1992, 2833.
Firouzabadi. K; Sharifi, A. Synthesis, 1992, 999.
Section 168
Ketones from Alcohois
03 OH
RuCI2(PPh3)3 acetone , 1 h
(IIIWO)
225
-
91%
Wang, G-Z.; Backvall, J-E. 1. Chem. SOC., Chem. Commun., 1992, 337.
@
20% SbCl5,2OoC, 3 h
83%
- -
Harada, T.; Mukaiyama, T. Chem. Lett., 1992.81.
CuBr2 - LiOt-Bu , THF , RT
-
94%
also for preparation of aldehydes from 1' alcohols
Yamaguchi, J.; Yamamoto, S.; Takeda. T, Chem. Lett.. 1992, 1185.
9NC'k0
C1-N
k Yc1
0
OH
Py ,acetone
-
0
G.A.; Nalbandy, M. Synth. Commun., 1992, 22, 1589.
REVIEWS :
"Synthetic Oxidations with Hypochlorites"
Skarzewskl.,Siedlecka, R. Org. Prep. Proceed. lnt.. 1992, 2 4 , 6 2 5 . Related Methods: Section 48 (Aldehydes from Alcohols and Phenols).
SECTION 169: KETONES FROM ALDEHYDES CHO 1. 1.5 eq. AlMez(BHT)(OEt2) PhMe , 1.Sh
BHT = 2,6-di-t-buty1-4-methylphenol Power, M.B.; Barron. Mi. Tetrahedron Lett., 1990, 31, 323.
quant.
85%
226
Compendium of Organic Synthetic Methods, Vol8
Section 169
CO~(CO)E, PY,12 h stainless steel autoclave (CO:H2 - 10 MPa)
PhLCHo
60%
Fontaine, M.; Noels. A.F.; Demonceau, A.; Hubert, A.J. Tetrahedron Lett., 1990. 31, 3117.
fi
1. BuLi , t-BuONa
THF , -78°C
MEM OBn
2. Me1 , -78°C
OBn
n
also reacts with aldehydes
97%
Lloshutz.;Garcia, E. Tetrahedron Lett., 1990, 31, 7261.
@-o
0
, c o , 200°C
PhCHO
R U ~ ( C O )48 I ~h,
Kondo, T.; Akazome, M.; Tsuji, Y.;
l!mmkJ,
50%
J. Org. Chem., 1990, 55, 1286.
1. (MejSi)zC(Li)OMe THF
n-C9HlGH0
2. HCI ,aq. THF
-
0 n-C9H19
75%
Yoshida.; Matsunaga, S.;Ishichi, Y.; Maekawa, T.; ISQLLJ. Org. Chem., 1991. 56, 1307.
Me3Si0 Ph
0
PhCHO
Me
iPro 0
C02H
20% &l O+C0,H*BH3-THF OiPr
OH
OSiMe3
P h v P h ph
86%
(955 erythro:threo) (85% ee , R)
Furuta, K.; Maruyama, T.; Yamamoto. H,J. Am. Chem. SOC.,1991. 113, 1041.
Ketones from Amides
Section 171
SECTION 170:
227
KETONES FROM ALKYLS, METHYLENES AND ARYLS
This section lists examples of the reaction, R-CH2-R'
0 --L C0,Et
2
R(C=O)-R'.
+CO,Et
CHlClz , 0°C 2. TEA, PhH , 2 5 T
0
good yield
Hoffman. R.V,; Kim, H-0.; Wilson, A.L. J. Org. Chem., 1990, 55, 2820.
SECTION 171: KETONES FROM AMIDES 0
n-C6H f N . OMe Me
Bergman, R.; Nilsson, B.;
Ms
(y
1.
ether
9
RT
2. H2O 3. wet silica 86% Tetrahedron Left.,1990, 31, 2783.
1. TFAA , DCE
2.6-di-t-butyl-4-methyl pyridine
2. 83OC
H
3. H20/CC14, reflux
88%
(98% ee)
Chen, L.; Ghosez. L, Tetrahedron Lett., 1990, 31, 4461. I-BuLi ,THF -7WC -+ -20°C
he
Souchet.;Clark, R.D. SynLeft, 1990, 151.
1
Ph
NEtz
1. sec-BuLi , TMEDA 2.
OBr
CHO
3. t-BuLi ; -78T -+ RT 4. air
Wang, X.; Snieckus. \L SynLett, 1990, 313.
*
& /
0
60%
Section 172
Compendium of Organic Synthetic Methods, V 01 8
228
.OMe
MeQNli;" Me'
1.5 eq. PhMgBr ,THF
0°C , 1 h
Me
0
4 eq. PhMgBr ,65OC, 7 h
0
* p h f l N OMe 95% 0 Me
-
+
21%
P+Ph 62%
Sibi. MP,;Sharma, R.; Paulson, K.L. Tetrahedron Letr., 1992, 33, 1941.
SECTION 172: KETONES FROM AMINES 1. H2, TFA, PtO2
2. Me1
3. Na , EtOH 4. H20 Stevens, R.V.; Canarv. J.W, J. Org. Chem., 1990, 55, 2237.
Me
#N-NMe*
MMPP-6 H 2 0 , MeOH pH 7 buffer, 0°C , 5 min
0
0
76%
MMPP = magnesium monoperoxyphthalate Bnders, D,; Plant, A. SynLert, 1990, 725.
Ph
-T
N-J Pi
1. PhCH=NPh , DMF t-BuOK, 75°C * 2. aq. H+
+
7 N-H PK
P h r P h 0
94% Paventi, M.; Hav. A S , Tetrahedron Lett., 1991, 32, 1617.
PhYPh
Fe(C104)3, MeCN
"OH
Ir
PhKPh II
0
79%
Kumar, H.; Kaur, B.; Kumar. B. Ind. J. Chem., 1991, 308,849.
Ph
PhIClz , Py , CHC13
FN-OH
1O"C, 3 h Radhakrishna, AS.; Augustine, B.; Sivaprakash, K.; 1473.
75%
Synth. Commun., 1991, 21,
Ph)= Me
229
Ketones from Esters
Section 173
6 eq. KHSO5 ,acetone
N- N H n
0 PhlMe
99%
10°C. 24 h * Synth. Commun., 1992, 22, 1583.
Jung, J.C.; Kim, K.S.;
DMSO , Me3SiCl MeCN , reflux
Ph
e
Ph
0 , , ) ,
98%
Ghelfi, F.; Grandi. R,; Pagnoni, U.M. Synth. Commun., 1992, 22, 1845.
0
2 eq. (Me$i0)2CrO2
N-OH
CH2C12
Lee., Kwak, K.H.; Hwang, J.P. Synrfi. Commun., 1992, 22, 2425. N - N H T ~ Na2C03- 2 H202 ,4OoC * DMF - H20 PhA Me Narayana, C.; Reddy, N.K.;
Ph
quant.
i
82%
Me
Synth. Commun., 1992, 22, 2587.
SECTION 173: KETONES FROM ESTERS 02CEt
Bacillus coagulans 0.2 M phosphate buffer pH 6.5, 30°C, 18 h
BnO
BnO
OBll
26% (95% ee) Matsumoto, K.; Suzuki, N.; Q&I,H,Tetrahedron Lett., 1990. 31, 7159. AI(SiMe3)3 , THF 1.1eq. CuCN , 0°C +
Ph
Me
57% (42% ee)
0 Me
SiMe3
82%
Nakada, M.; Nakamura, S.; Kobayashi, S.; Ohno. M, Tetrahedron Lett., 1991, 32,4929. OSiMel
Ph-0
K 0
C1
4
Ph
-,AgOTf
CH2C12
*
Phd P h
87% Takeda. K,; Ayabe, A.; Kawashima, H.; Harigaya, Y . Tetrahedron Lett., 1992, 33, 951.
230
Compendium of Organic Synthetic Methods, Vo18
1. 1.4 Fez(C0)g ,ether 2. BF3*OEt2,CHzC12
OAc
0 OSiMe3
h C O , E t
3. Me3N-O
Section 174
EC0& 71%
(1 :1 diastereomer ratio) Qggn. J.R;Carroll, M.K. Tetrahedron Lerf., 1991, 32, 1141.
DCA (h = 450 nm) MeCN [photoinduced electronic transfer]
ph3
Me3Si0
*
38%
DCA = 9 . 1 0 - d i c y a n o a n t e
Tetrahedron Left., 1992, 33, 1973.
Heidbreder, A.;
L
Pichia farinosa 0.2 phosphate buffer pH6.5,30min
*
b+& S
74% (55% ee) Kume, Y.;
23%
Tetrahedron Len., 1992, 33, 6367.
SECTION 174:
KETONES FROM ETHERS, EPOXIDES AND THIOETHERS
Meom AgOTf
SPhSPh
-;-
CHZC12
Ausr. J. Chem., 1990, 43, 815.
Chen, K.; Koser. G.F. J. Org. Chem., 1991, 56, 5764.
95%
0
Ketones from Halides
Section 175
23 1
t-BuMe,SiO MeCN , 0°C
+
*
1)
(>20
Snider. B.B.; Kwon,T. J. Org. Chem., 1990, 55, 4786.
87%
BnBr , THF , 2 0 T Bu4N+(Ph3SnFzJ 6h
99%
.
Ginma.. M, Tetrahedron Lett., 1991, 32, 7381.
OSiMeB
AgOzCCF3, BuI CHzC12 -78°C -+ 25°C
*
a:u 56%
Jefford, C.W.; Sledeski, A.W.; Lelandais, P.; Boukouvalas, J. Tefrahedron Lett., 1992, 33, 1855.
SECTION 175:
KETONES FROM HALIDES AND SULFONATES
&
Reid.; Reny Runge, J.M.Tetrahedron Lett., 1990, 31, 1093. Br
=/OBu ,
NEt3
91%
Me
TIOAc , DMF 100°C , dppe 91% Cabri.;Candiani, I.; Bedeschi, A.; Santi, R. Tetrahedron Lett., 1991, 32, 1753. I . Zn* ;CuCN.2 LiBr
" 2. BzCl also for conjugate addition Zn* = ZnCl2Li naphth. reaclions and reaction with ArX Zhu, L.; Wehmeyer R.M.; &&g. R.D. .I. Org. Cherii., 1991, 56, 1445.
92%
0
232
Section 175
Compendium of Organic Synthetic Methods, Vol8
n Me Kraus. G .At; Hansen, J. SynLett, 1990, 483. OBu
, Pd(0Ac)z PhxMe dppp , NEt3 , DMF * 0 90% 80"C, 3 h 2. H+ Cabn.;Candiani, I.; Bedeschi, A.; Pence, S.; Santi, R. J. Org. Chem., 1992, 57, 1481.
Ph-oTf
1.
=/
S02Tol t-BuOK ,THF , -78°C
81% 3740.
D.R; Robinson, LA.; Amato, G.S.; Osterhout, M.H. J. Org. Chern.. 1992, 57, 1. Li ,ZnCl2 , 0°C
UBr
2. C13CCOCI ))I)))) = O"C+ 23°C Core?. E J.; Link, J.O. Tetrahedron Lett., 1992, 33, 3435. /
/
1.
4
n-Ck!H17,B
mCC 82%
, I - B u - N S , K3P04
Pd(PPh3h
+
2. H3O+
0 Ph'Lc n-C*H,, 97%
Ishiyama, T.; Oh-e, T.; Miyaura, N.; Suzuki, A. Tetrahedron Lett., 1992, 33,4465. Related Methods:
Section 177 (Ketones from Ketones). Section 55 (Aldehydes from Halides).
Ketones from Hydndes
Section 176
233
SECTION 176: KETONES FROM HYDRIDES This section lists examples of the replacement of hydrogen by ketonic groups, R-H + R(C=O)-R'. For the oxidation of methylenes, R2CH2 -+ R2C=O, see section 170 (Ketones from Alkyls).
(y N
-
O'K 0 CF3
AICl3
F3C
sM Qo H
61%
Shimada, M.; Takahashi, M.; Kitajima, H. Chem. Left., 1990, 783.
;-
Asvanpar.;Lahoti, R.J.; Srinivasan, K.V.; Daniel, T. Synthesis, 1991, 322.
ArMe gives ArcHO Firouzabadi. H,; Salehi, P.; Sardarian, A.R.; Seddighi, M. Synrh. Commun., 1991, 21, 1121.
xi
n-CsH11 0
n-CsH11
10%GaC13,20% AgC104 CH2C12, RT ,20 h
Me0
n-C5H 1 1
Me0
91%
Mukaiyama, T.; Ohno, T.; Nishimura, T.; Suda, S.; Kobayashi, S. Chem. Left., 1991, 1059.
Ph-
Ph
t-BuOOH Cr-pillared montmorillonite
0
* p h A ph
90%
Choudarv. B.M.; Prasad, A.D.; Bhuma, V.; Swapna, V. J. Org. Chem., 1992, 57, 5841. A c ~ OCH2C12 , 4% SbCl5 ,30 min
1 eq. LiC104
MeOO -Me 89%
Mukaiyama, T.; Suzuki, K.; Han, J.S.; Kobayashi, S. Chem. Lett., 1992, 435
234
Section 177
Compendium of Organic Synthetic Methods, Vol8
SECTION 177: KETONES FROM KETONES This section contains alkylations of ketones and protected ketones, ketone transpositions and annulations, ring expansions and ring openings and dimerizations. Conjugate reductions and Michael alkylations of enone are listed in Section 74 (Alkyls from Alkenes).
For the preparation of enamines or imines from ketones, see Section 356 (Amine-Alkene).
Do
Me
excess Me1 ,DMSO
KOH (solid) 60°C
M e Me 90% Langhals, E.; Lanehals. H, Tetrahedron Lett., 1990, 31, 859.
<siMe3
m:u
PhMe.4; ~
~
0
74%
1
6
Bu SPh also with Cr(C0)6 Choi, Y.R.; Kim,B.J.; Jeong, J.U.; Lee, S.; Lee, J.H.; Pyun, C. Tetrahedron Lett.,
m;
1990, 31, 2713.
1. Pb(OAc)4, Hg(0Ac)z ,CHC13
PhB(0H)Z 2. py '
-
$c,,
&E02Et
774
Morgan, J.; Pinhev. J.T,J. Chem. Sac., Perkin Trans. I, 1990, 715. 1. hv ,hexane 2. 150°C
Me
-+ 45%
-M.;Arai, M.; Nishizawa, K.; Hasegawa, T. J. Chem. SOC.,Chem. Commun., 1990, 374.
1. LDA , THF , -78°C 2. BuLi , -78°C -+ 0°C
3.n-CsH11Br -78"~3 -20°C 71% A u-n Nakahira, H.; Rvu. L;Ikebe, M.; Kanbe, N.; Sonoda. N,Angew. Chem. Int. Ed. Engl., 1991, 30, 177.
SnBu3
Section 177
Ketones from Ketones
OSiMe, I
235
0
1. Meti-LiBr ,ether
II
(92% ee , R)
3. BnBr , PhMe
Murakata, M.; Nakajima, M.; %ma. & J. Chern. Soc., Chern. Conmun., 1990, 1657.
0
1.2.5 LDA , THF 10 HMPA , O°C
0
Me
2. Me1 , -78°C
Me Me
R = Li
s95 80 >95
= Bn
= Bz
5 20
(34%) (90%)
5
(79%)
Mdhrvev. G.J.; Andersen, M.W. Teirahedron Lett., 1990, 31, 4569. CDCN , KF.2 1120 (Ph3SnbTeI5 h
Li, C-J.;
m.D.N Tetrahedron Lett., 1991, 32, 1545. anhydrous FeC13 on S i 0 2 , CH2C12
mo
8
63%
Patnev. H.K. Tetrahedron Lett., 1991, 32, 2259.
+g,, 0
Rhz(OAc), , RT CHzClz, 12 h
+ +
Me
0
85%
Sonawane. H.R,; Bellur, N.S.; Ahuja, J.R.; Kulkami, D.G. .I. Org. Chern., 1991, 56, 1434.
6 0
1. "-N(h
,DMI;
NEti , 3 h , h v (sunlamp) 2.H30'
Russell. G.A.; Wang, K. J. Org. Cbent., 1991, 56, 3475.
90%
Compendium of Organic Synthetic Methods, Vol8
236
Section 177
SmI2, THF ,DMPA
DMPU = 1,3-dirnethyl-3,4,5,6-tetrahydro-2( 1H)-pyrimidinone Batey, R.A.; bbhawell. W.B. Tetrahedron Lett., 1991, 32, 6211,6649.
*Q+w
reflux
slow addition (7-10 h)
18% 0
of 3.3 eq. BusSnH with
0 74% AIBN to PhH Dowd. P.; Zhang, W. J. Am. Chem. Soc., 1991, 113, 9875. Zhang, W . ;Dowd. P. Tetrahedron Lett., 1992, 33, 3285. 0
M~
1. EtAlCh , CHzC12
RT,16h
-
2. H 2 0
H Fujiwara, T.; Tomaru, J.; Suda, A.; Se , H 2 0 , DBU CO (30 atm) , 120°C
P
h 0
b
24 h
33. 6347.
Do 77%
H
(93:7 cis:trans)
Tetrahedron Lett., 1992. 3332583.
L + PhM
Ph
10%
m; Inoue, J.; Teranishi, K.; Moriwaki, M.; . .
82%
Tetrahedron Lett., 1992, 33, 331 1.
LaumLLL;
3%
Tetrahedron k t t . , 1992,
Satoh, T.; Itoh, N.; Gengyo, K.; Yamakawa. K , Tetrahedron Letf.. 1992, 33, 7543.
Section 179
Ketones from Alkenes
aC>
237
Related Methods: Section 49 (Aldehydes from Aldehydes).
SECTION 178: KETONES FROM NITRILES
N
1. Cp2Zr-propyleneI"Cj~Zr" 2. H30'
-
-is
d
M Ts
e 54%
Mori. M.; Uesaka, N.; Shibasaki, M. .I. Chem. SOC.,Chetn. Cornmun., 1990, 1222.
SECTION 179: KETONES FROM ALKENES 2% Pd(OAc)z, aq. MeCN 90% benzoquinone
0.24M ~
*Y 1 0 ~
~
82%
Miller, D.G.; Wavner. D.D.M.J. Org. Chem., 1990, 55, 2924.
Eilbracht.;Hiittmann, G-E. Chem. Ber., 1990, 123, 1053. Ellbracht.;Hiittmann, G-E.; Deullen, R. Chem. Ber., 1990, 123, 1 0 6 3 . cat. RuO2 ,MeCHO , 3 h acetone , 0 2 ,40°C pyromellitic acid
*
0""
77%
pyromellitic acid = 1,2,4,5-benzenetetracarboxylicacid
Kaneda. K.; Haruna S.; Imanaka. T.; Kawamoto, K. J. Chem. SOC., Chem. Cornmun., 1990, 1467 CO (75 atm) , 80°C, 3 h Bu3SnH, AIBN ,PhH
0.05 M (32:68
ZE)
&LL;Kusano, K.; Hasegawa, M.; Kambe, N.; Sonoda. N, J. Chem. Soc.. Chetn. Cornmun., 1992, 1018.
238
Compendium of Organic Synthetic Methods, Vol8
1. BH-j-THF ,THF ,2"C
2. PCC, CH2C12, reflux
Parish.;Parish, S . ; Honda, H. Synth.
/\/\/\// Ishiyama, T.; Miyama, N.;
-
Section 180
0, 77%
Commun., 1990, 20, 3265.
1.9-BBN 2. CO ,n-GH13I
x
.c
Pd(PPh3)4, hv K3P04, PhH ,RT 24 h
n-C6H 1 3
n-C8H 1 7
67%
Tetrahedron Lett.. 1991, 32,6923.
[PdCl(NO-J(MeCN)2] \CyCl2;32;p,4 m \ + \
15% CHO 48% DPA = N,N-diethyl pivaloyi chloride Kiers, N.H.; Ferinm. B.L.; van Leeuwen, P.W.N.M. Tetrahedron Lett., 1992, 33, 2403.
See also: Section 134 (Ethers from Alkenes).
SECTION 180:
Section 174 (Ketones from Ethers).
KETONES FROM MISCELLANEOUS COMPOUNDS
Conjugate reductions and reductive alkylations of enones are listed in Section 74 (Alkyls from Alkenes). Ketones from oximes are listed here.
gMe
Takeda, K.; Torii, K.; Qgura. H, Tetrahedron Lett., 2990, 31, 265. TMSCl ,NaNO2 ,CC4 5% Aliquat 336 , RT , 5 h
&Me 95%
Lee. J.G,; Kwak, K.H.; Hwang, J.P. Tetrahedron Lett., 1990, 31, 6677.
Me&
bc.0 H
1. PhCeCI2, THF , -78°C 2. aq. NH4CI. -78°C -+ RT
0 * Me3SidPh
Kits.; Matsuda, S.; Kitagaki, S.; Tsuzuki, Y.;Akai, S. SynLett, 1991, 401.
79%
Section 180A
MeO.
Protection of Ketones
1
239
Li, THF
"OMe
-78"C+ 22°C 2. B u t i , -78°C 422°C
h e Me
99%
Whipple, W.L.; Reich. HJ. J. Org. Chem, 1991, 56, 2911. 1. PhCH=CFZ 2. Ni(R)
W N . @
>q H "'
0
0
29%
Ph'
Purrineton.~.~.; Sheu, K-W. Tefrahedron Lett., 1992, 33, 3289. 1. c02 2. PhLi
3.aq. NH4CI Zadel, G.;
92%
Angew. Chem. lnt. Ed. Engl., 1992,31, 1035.
SECTION 180A: PROTECTION OF KETONES e' , wet MeCN Ptanode.1.30V
sUs
70% Martre, A-M.; Mousset. G,; Be1 Rhlid, R.; Veschambre, H. Tetrahedron Lett., 1990, 31, 2599.
0;:
10% SiH212, CHCI3 -42oc, l m i n
99% Keinan. EL;Perez, D.; Sahai, M.; Shvily, R. J. Org. Chent.. 1990, 55, 2927.
0
[ZrOcl2*8 H 2 0 , aq. NaOHl ethylene glycol
74%
W a k i . M,; Takahashi, K.; Kuno, H.; Matsushita, H. Bull. Chern. Soc. Jpn., 1990, 63, 1258.
240
Compendium of Organic Synthetic Methods, Vo18
SEt
GaC13, MeOH , 0 2
SEt
CH2C12, RT , 2 4 h
*
P
h
Section 180A
o
O
71%
Hashimoto, Y.; Kihara, N.; Umehara, H.; Hasegawa, M. Chem Lett., 1990, 831.
o(3
HSCHzCHzSH, PhMe activated bentonite, 5 h
99%
Miranda, R.; Cervantes, H.; Joseph-Nathan, P. Synth. Commun., 1990, 20, 153. sulfonated charcoal PhH , reflux 98%
Patney, H.K. Tetrahedron Lett., 1991, 32, 413.
Q
2 [EtSH , TeC141 C4H4C12, RT
m,H.; Masumoto, K.; Inamasu, T.; &&i&Tefrahedron , Lett., 1991, 32, 2039. hn (>360 nm) , 0 2
6h
Klunata.;Kato, Y . ; Hasegawa, E. Tetrahedron Lett., 1991, 32, 4349.
n Ph&
Me
1. SbCl=, , CH2C12,O"C 2. aq. NaHC03,O"C w
0
Ph
4Me
Kamata. M.; Otogawa, H.; Hasegawa, E. Tetrahedron Lett., 1991, 32, 7421.
78%
24 1
Protection of Ketones
Section 180A
hydroxy apatite, 1 h (Et0)3SiH , heptane 99% hydroxy apatite = [Ca10(P04)6(OH)21 Izumi., Nanami, H.; Higuchi, K.; Onanaka, M. Tetrahedron Lett., 1991, 32, 4741. 1. TMSOTf , Me2S
CH2Cl2 , -78°C
2. TMSOTf * TMSOCH2CHzOTMS 3. aq. K2CO3
CHO
E
C
H
O 80%
Kim.; Kim, Y.G.; Kim. D. Tetrahedron Letr., 1992, 33, 2565. acetone-CH2CI2 0°C , 2 4 h
>95% 98% conversion D'Accolti, L.; Fiorentino, M.; Fusco, C.; Adam. W,;Gonzhlez-Nufiez, M.E.; Mello, R. Tetrahedron Lett., 1992, 33, 4225.
w;
Ph
s s''Me3 U
e- (P(electrodes)
t
Ph 9SiMe,
0
NaC104, aq. MeCN
95%
Suda. K,;Watanahe, J.; Takanami, T. Tetrahedron Lett., 1992, 33, 1355.
pS
hv (visible), MeCNIH20 methylene green
*
p i y Me
u; Wang, Q. Tetrahedron Lett., 1992, 33, 5909. ~
G
.
A
Ph
1
91%
Me
.Wang, ; Q. SynLert, 1992, 335.
Ph
SEt
x SEt
DMSO , 140°C.4 h
Me
Rao, Ch.S.; Chandrasekharam, M.;;&&I
t
Ph
2.0
94%
Me
m i p p a . H, Tefruhedron Lett.. 1992, 33, 8163.
See Section 362 (Ester-Alkene) for the formation of enol esters and Section 367 (Ether-Alkenes) for the formation of enol ethers. Many of !he methods in Section 60A (Protection of Aldehydes) are also applicable to ketones.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
13
PREPARATION OF NITRILES
SECTION 181: NITRILES FROM ALKYNES NO ADDITIONAL EXAMPLES
SECTION 182: NITRILES FROM ACID DERIVATIVES NO ADDITIONAL EXAMPLES
SECTION 183: NITRILES FROM ALCOHOLS AND THIOLS (NiSO&S208-NaOH) NH3, HzO
Ph-OH yamazaki.;Yamazaki,Y. Chem. Lett., 1990, 571.
*
PhCN
82%
SECTION 184: NITRILES FROM ALDEHYDES P h x ' N Moore, J.S.;
NMe,
1. Me1 , 150 min 2. DBU ,25"C
-
Ph3(""
83%
J. Org. Chem., 1990, 55, 3314.
PhCHo 2.5 KZS20g
*
PhCN
+
PhCOOH 11%
82% horn, P.K.; Savre. L.M, Tetrahedron Lett., 1991, 32, 1007.
PhCHO
(NiS04/K2SzOg-NaOH) NH3. HzO
Yamazaki.; Yamazaki, Y. Chem. Left., 1990, 571.
PhCN
76%
Section 187
243
Nitriles from Amines
Mexican Bentonite
PhCHO
rn
PhCN 50% microwaves (2450 MHz) Delgado, F.; Cano, A.C.; Garcfa, 0.: Alvarado, J.; Velasco, L.; Alvarez. C,; Rudler, H. Synth. Commun.,1992, 22, 2125.
SECTION 185: NITRILES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 186: NITRILES FROM AMIDES
0 P h A N V
Ph3PBr2, NEt3, RT CH2C12,lO h
H
c
Ph
89% Walters. M.A,; McDonough, C.S.; Brown, P.S. Jr.; Hwm, A.B. Tetrahedron Lett., 1991, 32, 179. 1. CBr4, PPh3 , MeCN R T + reflux
0 Ph
. )
Ph-CN
NHOMe 2. Zn ,DMF , AcOH reflux
Sakamoto, T.; Mori, H.; Takizawa, M.;
69%
Synthesis, 1991, 750.
SECTION 187: NITRILES FROM AMINES
OH
?!
i
J! H Et
K 0
EtO
l*
2. heat
CN
,MeCN , cat. NJ33 25 "C
-
C t
PM
liL-Ll*
95%
Thomas.;Greyn, H.D. Synthesis, 1990, 129.
GN-OH 4 eq. PPh3,2 eq. CC4
MeCN , RT
c1
$C=N
97%
c1
Kim, J.N.; Chung, K.H.; Rvu. E.K. Synth. Commun.,1990, 20, 2785.
244
Section 191
Compendium of Organic Synthetic Methods, Vol8
KSF , montmorillonite ,PhMe
Phh
b
N- OH
reflux, 15 h Meshram. H.M, Synthesis, 1992, 943.
Ph-C=N
70%
SECTION 188: NITRILES FROM ESTERS NO ADDITIONAL EXAMPLES
SECTION 189:
NITRILES FROM ETHERS, EPOXIDES AND THIOETHERS
M e 0 OMe Ph Ph
TMS-CM , RT , 5 h [Rh(COD)CI]z
Me0 CN 86% Ph + p h T,Bull. Chem. SOC.Jpn.,
Soga, T.; Takenoshita, H.; Yamada, M.; Han, J.S.; -a.
1991, 64, 1108.
Mukaiyama, T.; Takenoshita, H.; Yamada, M.; Soga, T. Chem. Lett., 2990,229 (Z product].
SECTION 190: NITRILES FROM HALIDES AND SULFONATES 2 eq. KCN ,dppf ,NMP 2% Pd2(dba)3*CHC13
*
0..
96%
Takaei.~.; Sasaki, K.; Sakakibara, Y. Bull. Chem. SOC.Jpn., 1991, 64, 1118. SECTION 191: NITRILES FROM HYDRIDES AICI3, CS2 -70°C + 0°C
L
CEN 51%
Bultke, K.; Reiher, T.;
-
0
Synth. Commun., 1992. 22, 2231.
SECTION 192: NITRILES FROM KETONES Preparations of nitriles from oximes and hydrazones, which are ketone derivatives, are found in Section 195. NO ADDITIONAL EXAMPLES
245
Nitriles from Miscellaneous
Section 195
SECTION 193: NITRILES FROM NITRILES Conjugate reductions and Michael alkylations of alkene nitriles are found in Section 74D (Alkyls from Alkenes). HCHO , H2 (CO) , DMF cat. R u ~ ( C O ) I Z230°C , * 16 h
Ph 7CN
86%
CN
Chem. Lett., 1990, 765.
A h , F.; Hayashi, T.;
Rhodococcus phosphate buffer butanica *
A
Ph*Me
P
C
N +
P
3OoC, 3 h
C /
0.1% substrate 56% (27% ee)
30% (95% ee)
Kakeya, H.; Sakai, N.; Sugai, T.; Q h J L Tetrahedron Lett., 1991, 32, 1343. K2C02, EtBr
Ph-CN
c
Ph
1"+
Et
PhfCN
Et
Et 16% 58% Xu. C.Z.; Mao, X.J.;Shen, H.B.; Chen, W.Q. Org. Prep. Proceed. lnt., 1991, 23, 153.
SECTION 194: NITRILES FROM ALKENES NO ADDITIONAL EXAMPLES
SECTION 195:
NITRILES FROM MISCELLANEOUS COMPOUNDS
The preparation of nitriles from oximes and other compounds are presented here.
Ph
xN.
OH
1. AII3 , MeCN 82°C , 2 h
2. H 2 0
c
Ph- C=N
92%
Konwar, D.; B o ~ a hR.C.; , Sandhu. J.S. Tetrahedron Lett., 1990, 31, 1063.
N
246
Compendium of Organic Synthetic Methods, Vol8
Section 195
Sn(SPh), , PBu3 , DEAD
n-C11H23
n-CiIH23-CN
DMAP , CHzClz ,(lo(? 10 min Urpi, F.; Vilarrasa, J. Tetrahedron Lett., 1990, 31, 7499.
0-
N.NHBz
98%
e- (0.7 V) ,2.2F/mol NaCN ,MeOH Pt electrodes
- OCN 70%
Okimoto, M.; f2hihaL J. Org. Chem., 1990, 55, 1070.
Ph-N=(
c1 c1
e- , Hg cathode, Pt anode DMELiCIO4, Na2C03 15°C
c
Ph- NEC
91%
Gulrado.;Zapata, A.; Fenor, M. Tetrahedron Lett., 1992, 33,4119. REVIEWS :
"TheIsocyanide-CyanideRearrangement;Mechanism and Preparative Applications" Meier, M.; Haaf, K.; Pakusch, J.; Wolber, E.K.A.; Miiller, B. Angew. Chem. Inf. Ed. Engl., 1991, 30, 893.
;-
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
14
OF ALKENES
PREPARATION
SECTION 196: ALKENES FROM ALKYNES n-C5H11 - CE C-n-C5H
1. M l 5 , HMPARHF PE T a c h , Zn ,DMElPhH
2. aq. NaOH
n-C5Hl n - C 5 ~ I , d
Nb 74% (>99:1 2:E) Ta 85% (>99:1 Z:E) Kataoka Y.; Takai. IL;Dshima. K.; Utimoto. K Tetrahedron Lett., 1990, 31, 365. 1. t-BuLi , hexane/ether -78°C -+ 25°C
99
1)
9
90%
59%
Inanaea.,Yokoyma, Y.; Baba, Y.; Yamaguchi, M. Tetrahedron Lett., 1991, 32, 5559.
(p
Bu3SnH , LiCl , DMF 5% Pd(PPh3)4 , 60°C
OTf
C.H
8h
Bu
Luo. F-T,; Wang, R-T.Tetrahedron Left., 1991, 32, 1103. 1. HB(c-C6H11)2,THF
Ph- C: C- SiMe,
Ph
0°C 4 25°C
w
2. PhBr , THF , NaOH Pd(PPh314, reflux 3. NaOH ,H202
phr-( SiMe,
Soderauist. J.A; Le6n-C016n, G. Tetrahedron Lett., 1991,32,43.
40%
57%
250
Compendium of Organic Synthetic Methods, Vo18
P h . C : C n B r
Section 196
1.5 eq. S d z , THF,24 h
60%
reflux
Bennett.;Larouche, D. SynLett, 1991, 805. 7% Co(acac)3 , dppe 6 eq. Et2AlCl
CEC-H
78%
Lautens.;Tam, W.; Edwards, L.G. J. Org. Chem., 2992,57,8. n-C3H,-CE C- H
1. cat. Zr porphyrin Et3A1, 55 h
- n-C3H7F
2. Ht
Shibata, K.; Aida, T.; Jnoue. S , Tetrahedron Lett., 1992, 33, 1077.
26%
Et
CpzZr(H)CI , THF
u s h u t z . B.H,; Keil, R.; Barton, J.C. Tetrahedron Lett., 1992, 33, 5861. u t z . B.H.; Keil, R.; Ellsworrh, E.L. TetrahedronLett., 2990, 31, 7257.
Ph
Ph
1.4 eq. Mg ,THF 2. Cp2TiCI2,CH2CI2
(5
Ph
I.,
C (96
Harms, A.E.; &&J&
4)
42%
Tetrahedron Left.,1992, 33, 6565. 1. TMSCl ,Nal ,H20
H- CI C- Ph
MeCN
+
2. BuZnCl ,cat. Pd(PPh&
Ph
*
B~
54%
Luo.; Fwu, S-L.; Huang, W-S. TetrahedronLett., 1992, 33, 6839.
Tour. J . K ; Pendalwar, S.L.; Kafka, C.M.; Cooper, J.P. J. Org. Chem., 1992, 57, 4786.
Alkenes from Alcohols
Section 198
25 I
SECTION 197: ALKENES FROM ACID DERIVATIVES 10 eq. Tic13 , THF
PhKC1 0
5 eq. LiAlH4,ll h
w
Ph
Ph
Ph
+
+
w
18% Ph
74% Bull. SOC.Chim. Belg., 1991, 100, 375,
Dang, Y.;
SECTION 198: ALKENES FROM ALCOHOLS AND THIOLS 1. TMSCl , HMDS
2. L i t NH3 3. NH4CI
Ballester, P.; Cap4 M.;
Ph G
02s P
-
a J.M. Tetrahedron Lett., 1990, 31, 1339. h
SmI2, THF
--
’
Ph
Ph
)” Me’
Nd
82%
Kende. AS,; Mendoza, J.S.Tetrahedron Lett., 1990, 31, 7105.
phbCH0
1. Me3GeCH2C02bBuLDA THF , -78°C 2. H20, -78°C 3. BF3aOEt2, CH2C12 , 4 h
also with ketones Inoue, S . A m . L J. Org. Chem., 1991, 56, 437.
kH
n-C16H33
BF3aOEt2, CHzClz 25°C. 10 min
*
E:Z)
(8:l
P
h
’ w
C02t-Bu 80%
ny33 7” (79:21 E:Z)
+
(95
5)
90%
Posner. ; Shulman-Roskes,E.M.; Oh, C.H.; Carry, J-C.; Green, J.V.;Clark, A.B.; Dai. H.; Anjeh, T.E.N. Tetrahedron Lett., 1991, 32, 6489.
Compendium of Organic Synthetic Methods, Vol8
252
0
EtO- OEt p - c1
CbzHN C O B . NaH ,THF 0 Berti, F.; Ebert.;Gardossi, L. Tetrahedron Lett.,
* CbzHN
SECTION 199: ALKENES FROM ALDEHYDES
PhCHO
t
-
QOBn
1992, 33, 8145.
(Me$i)2CHPh , TASF C H g l z , 2OoC, 1 h
Section 199
Ph
0
75%
Ph
92% (E:Z = 1:l)
TASF = tris-(dimethylamino)-sulfonium difluorotrimethyl siliconate Palorno.;Aizpurua, J.M.; Garcia, J.M.; Ganboa, I.; Cossio, F.P.; Lecea, B.; L6pez. C. J. Org. Chem., 1990, 55, 2498.
1. BuzTe , THF, 80°C 2. PhCHO
0
Ph3P-CHZI
Y -7.;Shi, L-L. Chem. Ber.,
Li, S-W.;
0
58%
1990, 123, 1441.
0
T.Synktt, 1990, 322.
PhCHO , BuLi , PhH 5 min
ph;3
Ph-CHzCH,
Ph3PMe Br , Na t-amyl alcohol mesitylene ,reflux
4CHO Tsunoda, T.; JIudlickv.
c
1 ) ) ) ) ) ) ) )
63%
- 3 .2 Ph
3) quant. Ph
(1
Low. C.M&SynLett,
1991, 123.
SiMe,Ph
YSnBu3
1. BuLi , THF ooc
j~~
2. TFA ,THF , RT 12 h
w
5 1% (61:39 cis:trans) Barrett. A.G.M,; Hill, J.M. Tetrahedron Lett., 1991, 32, 3285.
(from hexanal)
nC5H I 1
Alkenes from Aldehydes
Section 199
PhCHO
+ M~/”
253
ZnBr2, BuLi
ZnBr
Ph
Me
Ph
i+ NMez
68%
(86% ee , S)
HO
Qp-mlzer. W.; Radinov, R.N. Tetrahedron Lett., 1991, 32, 5717.
79%
Afonso, C.A.M.; Motherwe 11. W.B,; O’Shea, D.M.; Roberts, L.R. Tetrahedron Lelt., 1992, 33, 3899.
0
1. LDA ,
P h ’ S y F
Ph
. MsCl ,NEt3 3 . 3 eq. BuLi
F
70% Satoh, T.; Itoh, N.; On&, K.; Kitoh, Y . ; Yamakawa. K, Tetrahedron Lett., 1992, 33, 1483.
CHO
BugSnCHBr2, LiI CIc12, DMF , THF 25OC
Hodpson. D.M. Tetrahedron Lett., 1992, 33, 5603.
--
NbCl5, MeLi ,DME
PhCHO
Ph-Ph
quant.
Kauffmann. T.; Kallweit, H. Chem. Ber., 1992, 125, 149. Related Methods: Section 207 (Alkenes from Ketones).
SECTION 200:
ALKENES FROM ALKYLS, METHYLENES AND ARYLS
This section contains dehydrogenations to form alkenes and unsaturated ketones, esters and amides. It also includes the conversion of aromatic rings to alkenes. Reduction of aryls to dienes is found in Section 377 (Alkene-Alkene). Hydrogenation of aryb to alkanes and dehydrogenations to form aryls are included in Section 74 (Alkyls from Alkenes).
254
Section 202
Compendium of Organic Synthetic Methods, Vol8
DCE , MeCCl3 , AIC13 5OoC,30 m h
cr
98%
Ph
SynLett, 1991, 925.
Sonawane. H.& ; Sudalai, A.; Daniel, T.;
SECTION 201: ALKENES FROM AMIDES Section 65 (Alkyls from Alkyk). Section 7 4 (Alkyls from Alkenes).
Related Methods:
Godfrey, A.G.; G a n e m . J . Am. Chem. SOC.,1990, 112, 3717.
SECTION 202: ALKENES FROM AMINES PhMe
&?
&I%
02
Davis. F,A,; Chen, B. J. Org. Chem., 1990, 55, 360.
n-CloH21
Me3Si
&
NH2
1. iAmON0, gl. AcOH %
2. BF3eOEt2
n-CtoH21, w
62%
J. Org. Chem., 1990, 55, 4474,
P
Et02C
Br
CO2Et
Bu3SnH AIBN PhH ,reflux 9
N-NH SO2ME-
ME3 = 2-mesityl
Kim. S ; Cho, J.R SynLert, 1992, 629.
60%
255
Alkenes from Esters
Section 203
SECTION 203: ALKENES FROM ESTERS
ax%
1. MeLi ,ether , 0°C 2. MeCu ,O"C, 23 h
3. O"C+ 24°C
Me
(91% ee)
Denmark. S.E,; Marble, L.K. J. Org. Chem., 1990, 55, 1984.
C0,Bn
1, B u - C S - P ~ ( O A C ) ~ CHSlz-THF 2 3 T , 30 min 2. H2, Lindlar , PhH 23°C
* ( 9 5 5 Z:E) '
Hashimoto, S.; Miyazaki, Y.; Shinoda, T.; 1loo. OPh
76%
J. Chem. SOC., Chem. Commun., 1990,
Bu3SnH. AIBN
PhH,6h
*
boMe
4
63%
Me M.T.; Dudek, C.M.; Cheung, A.W-H. Tefrahedron Lett., 1992, 33, 181.
OCHO
Pd(acac)z, PBu3, PbH 1.[HCOOH/NEt3/PhH]
RT ,30min
2. Hfl
88%
t-Bu t-Bu Mandai. T.; Suzuki, S.; Murakami, T.; Fujita, M.; Kawada, M.; Tsuii. J, Tetrahedron Leff., 2992, 33, 2987.
SECTION 204:
ALKENES FROM ETHERS, EPOXIDES AND THIOETHERS CpzNb , THF, 12 h
MeOzC o-
- 7 8 O C 4 RT
Schobert. R.; Hohlein, U. SynLeff, 2990, 465.
* (97:3 2:E)
86%
Section 205
Compendium of Organic Synthetic Methods, Vo18
256
AcO
2. 10% KF overnight
40)
( 60
(1.2: 1 a$,
40%
(1:2 a$,
Marco-Contelles, J.L.; Femhdez, C.; Ghmez, A.; Martin-Lehn, N. Tetrahedron Lett., 1990, 31, 1467.
d,,. SiMe3
Ph
BuLi ,DME
-78°C -+RT
. P h w S i M e 3 3%
Ph-
Bu
(98:Z E:Z)
Ukaji, Y.;Yoshida, A.; m a w a . T, Chem. Letf.. 1990, 157.
&\
\ Bu RS%
1. r-BuLi 2. t-BuLi
SiMq
* /JBu
SiMe3 93%
(16534
EZ)
F Tetrahedron Lett., 1991, 32, 3457. Santiago, B.; Lopez, C.; Soderaut,t.J.A. Lopez, C. Tetrahedron Lett., 1991, 32, 6305.
;-
ALKENES FROM HALIDES AND SULFONATES
SECTION 205:
2 Et-I
1. r-BuLi, ether, -78OC 2. c12zIcp2
3.
25°C
(y
4. 2N HCI
general method - preparation of lo organolithium reagents Neglshl.,swanson, D.R.; Roussel, C.J. .I. Org. Chem., 1990, 55, 5406.
Ph
Ph
Br
cysteine , NazSeO3 H20,O"C , 5 min
ph&Ph
98%
the R,R-diastereomergave 0% yield of alkene
Yanada.; Yanada, R.; Meguri, H. J. Chem. Soc., Cheni. Conlmun., 1990, 730.
Alkenes from Halides
Section 205
PhCHCl,
iron (11) oxalate ,DMF , 1 h 160°C
--
257
PhCH=CHPh
92%
Khurana.; Maikap, G.C.; Mehta, S.Synrhesis, 1990, 731.
H.N$l
d SnBu3, PdAdbah
OA N H
P ( 2 - f ~ ~ l,)NMP 3 , RT 16 h
O
AN H
w.V.; Hauck, S.I. SynLetl, 1991. 157.
n 0 0
1 . 3eq. NaNH2 2.m3,ether
89%
n
< -50°C 69% 3. aq. NH4Cl Isaka, M.; Ando, R.; Morinaka, Y.; Nakamura, E. Tetrahedron Lett., 1991, 32, 1339.
c1
c1
1.2.2 r-BuLi ,ether, -100°C 2. CuBr.SMe2, AcCl 3.BuLi
*-
SiMe, 4 . X
Bu
X = TFA/TBAF X = KH,TBAF Barrett. A.G.M,; Flygare, J.A. J. Org. Chem., 1991, 56, 638.
94:6 E:Z)
5:95 E Z )
DMF , 160°C. 210 min
Ph&Ph
Ph
66%
Khurana.;Maikap, G.C. J. Org. Chem., 1991, 56, 2582. Khurana.;Maikap, G.C.; Sahoo, P.K.Synthesis, 1991, 827.
Larock.;Berrios-PeRa, N.G.; Fried, C.A. .I.
Org. Chem.. 1991, 56, 2615.
59% 57%
258
Compendium of Organic Synthetic Methods, Vol8
n-C5H11
Y
SiMe,Ph
c1
; .M.G.A-
1. Mg* (ether) 2. CuBr*SMez 3. BuCOCl 4. MeLi 5. x
*
n-C5H11
Section 205
==(
Me
Bu
X = TsOH 60% Mg* = activatedMag x=KH 61% Hill, J.M.; Wallace, E.M. J. Org. Chem., 1992, 57, 386. Cu (powder), MeOH Cu(C104)2*(H20)6
phHph Br Br
Ph
\==\
e
9
RT,4h Vijayashree, N.; Sapuelson. A.G Tetrahedron Lett., 1992, 33,559. /
\
OMS
NaI , Zn ,HMPA heat
(5:95 E:Z) (955 E:Z)
88%
Ph
82%
OMS
Ghosh.;Karpa, A.; Saha, G.; Paua, D. Tetrahedron Lett., 1992, 33, 2363. n-C&I 1-Br
*
S 0 2 P h . Zn , DMF
0.05 Co (porphyrin) ,20°C
c
&n-C6H11
85%
Giese.;Erdmann, P.; GBbel, T.; Springer, R. Terrahedron Lett., 1992, 33, 545.
SECTION 206: ALKENES FROM HYDRIDES For conversions of methylenes to alkenes (RCH2R' 200 (Alkenes from Alkyls).
0
Sakakura, T.; Abe, F.;
+ RR'C=CH2), see Section
RhCI(CH2=CH2)(PMe3)2 0.7 mm0Vdm3, 70°C hn (I > 375 nm), CH;?=CH2
(1 am)
turnover rate = 160 Chem. Lett., 1991, 297, 359.
Section 207
Akenes from Ketones
259
SECTION 207: ALKENES FROM KETONES I
0hira.s.Ishi, ; S.; Shinohara, K.; Nozaki, H. Tefrahedron Lett., 1990, 31, 1039.
%
1. t-BuLi 2. SOClZ
0
76%
Olah.G.A.; Wu, A.; Farooq, 0.;Surya Prakash, G.K. J. Org. Chem., 1990, 55, 1792.
($
+
$.&
Ph3P=CHC02EtI 70°C 4h
P h %+* Ph' 'OH
Me
A
enantioselectiveWittig-Homer in solid state
[43%ee (-11 I
Toda. F.; Akai, H. J. Org. Chem., 1990, 55, 3446.
Ph Ph
Po
CpzTiMeZ, PhMe ,65"C
*
Ph)= Ph
90%
Petasis. N.A.; Bzowej. E.I. J. Am. Chem. SOC.,1990, 112, 6392.
Ph
TIC14 , Hg , Mg ,THF
Po Ph
0°C + reflux, 2 4h
c
Ph
w y h Ph
87%
9
90%
Carroll, A.R.; Taylor, W.C. Aust. J. Chem., Z990, 43, 1439. 1. Me3SiCHzLi. ether 2. aq. H+
Ph
3. Nafion-H , CHzC12, RT l h
51%
Me
Olah.;Reddy, V.P.; Suva Prakash, G.K. Synthesis, 1991, 29.
P
h
260
Compendium of Organic Synthetic Methods, Vol8
1. LDA ,THF ;TfZNPh
O = C
N-Boc
-78OC-t O°C
2,
CI-
C
t
I
Section 207
-W
B
o
c
83%
Pd(PPhj)4, LiCl ,NazC03 DME , H2O ,reflux
a?)-
-
B(OH)~
Wusuow. D.J.; Wise, L.D. Synthesis, 1991, 993.
N
SOzMe
I . LDA , THF , -78OC 2. acetone
-w
poor yields with saturated aldehydes
51%
Baudin, J.B.; Hareau, G.;Julia.;Ruel, 0.Tetrahedron LeU., 1991, 32, 1175.
b”
1.9-BBN
2.NaOH ;Rangaishenvi, M.V.; Brown, H.C.; (&k 1991, 56, 1543. DME , TiC13Li , 16 h reflux
70% i. C.T; Hasha, D.L J. Org. Chem.,
*
Ph Me 83% E ; 9% Z
Nayak, S.K.; B a n e r u J. Org. Chem., 1991, 56, 1940. MeMgI , 18 h
c
Ph
70%
Ni, Z-J.; Mei, N-W.; Shi, X.; Tzeng, Y-L.; Wang, M.C.; Luh. T-Y. J. Org. Chem., 1991, 56, 4035.
W i s . N.A,; Bzowej, E.I. J. Org. Chem., 1992, 57, 1327.
6
Me
-
C
6
H
#?
O + PN.h
1. BuLi ,
Me
2. H20 3. AcOH
n
t
(91% ee ,R)
t-Bu Hanessian.;Beaudoin, S . Tetrahedron Lett.,
n
'b
26 1
Alkenes from Alkenes
Section 209
t-Bu 1992, 33, 7655, 7659.
Me3SiC(Nz)Li, THF -78°C -+ 0°C
0
n-C6H 13
Ohira. S,; Okai, K.; Moritani, T. J. Chem. Soc., Chem. Commun., 1992, 721. (Me-$iCH2)3TiCp
P
h
h
SiMe,
, PhMe
100°C
Akritopoulou, I. SynLett, 1992, 665. Related Methods:
Section 199 (Alkenes from Aldehydes).
SECTION 208: ALKENES FROM NITRILES NO ADDITIONAL, EXAMPLES
SECTION 209: ALKENES FROM ALKENES PhBr (sealed tube) Ph 75% OEt (E/Z 85/15)
OEt
Parrain, J-L.; Duchene, A.; Quintard. J-P. Tetrahedron Lett., 1990, 31, 1857.
Malane&;
cz:EF
1. n-CsH?MgBr, ether NiClz(dppe)
2. aq. NH4C1
-
Menicagli, R.; Lardicci, L. Gun. Chim. Itul., 1990, 120, 217
262
Compendium of Organic Synthetic Methods, Vol8
Section 209
1. 15% bpy*Fe(O)
PhH ,25"C , 3 0 min
OBn
2. cat. TsOH ethylene glycol
B ~ *
Takacs, B.E.; Takacs.& Tetrahedron Lett., 1990, 31, 2865. P-cyclodexuin , CeC13.7 H 2 0 CoC12, KCN , KCS , 24 h
-H
H2 (1 atm) , RT , 3 N NaOH
(98
85%
+>=( 2)
95%
Lee, J-T.; elper. H, J. Org. Chem., 1990, 55, 1854. 0
0
Me0
Verma, P.; Pav. S , l n d . J. Chem., 1990, 298, 652.
0
0
Me0
84%
,25"C, 14h
Me
Si02 , glass ampule
0
85%
Veselovskii, V.V.; Gybini, A S .; Lozanova, A.V.; Moiseenkov, A.M.; Smit, V.A. I n . Akad. Nauk. SSSR, 1990, 39, 107 (Engl., p. 94).
CH 2=C =CH,
1. Bu&n2/BuLi , CuCN THF , -78°C
2. Me1 , -78°C -+ 0°C *
Barbero, A.; Cuadrado, P.; Fleming, I.: Gonzdez, A.M.; Commun., 1990, 1030.
n-C6H 13 \=
C=
2 eq. C12AIH 5% PhB(OH)2
=r
M~SnBu396%
J. Chem. SOC.. Chem.
n-C6H13
\\
Nanahara. S,; Maruoka, K.; Doi, Y.; Yamamoto, H. Chem. Lett., 1990, 1595.
92%
263
Alkenes from Alkenes
Section 209
1. BuLi ,THF 2. t-BuOH, -50°C
/
Me3Si
~
Me3SiuBu
+
24 h
Me3s BU
3. BuI
(83
.. Degl’Innocenti, A.; Mordini. A; Pagliai, L.; Ricci, A. SynLett, 1991,
17)
155.
Fuchikami. T.; Ubukata, Y.; Tanaka, Y. Tetrahedron Lett., 1991, 32, 1199.
90%
IS)
(8 1 (94% ee, S )
Lamothe, S.; Chan. T.H, Tetrahedron Lett., 199
74%
92%
32, 1847.
1. Mg* , THF , RT
Ph A
P
h
-
2. -78°C + RT BrBr
Ph
Mg* = [MgC12/THF/Li naphth.]
65%
Rieke.; Xiong, H. J.
Org. Chem., 1991, 56, 3109; J. Org. Chem., 1992, 57, 6560. Xiong, H.; Rieke. R.D, Tetrahedron Lett., 1991, 32, 5269.
BuLi , THF
TsO
SnBu3
-20°C
+ 0°C
61%
Barbero, A.; Cuadrado, P.; Gonziilez, A.M.; h,!&JJ,; Rubio, R.; Fleming, I. Tetrahedron Lett., 1992, 33, 5841. 1. Cp$r(H)CI , THF
4n-C6H 13
2.Ph-O.
OEt OEt c a t . ~ u 0~ ~
y,’
Venanzi, L.M.; Lehmann, R.; Keil, R.;
?-
F%qH1’ +
(93
Phy n-C,H 7)
85%
Tetrahedron Lett., 1992, 33, 5851.
264
Compendium of Organic Synthetic Methods, Vo18
Section 210
pn-c8H 1.9-BBN 2. 3% Pd(PPb3k dioxane, THF K3P04,6o0C
Br
Miyaura, N.; Ishikawa, N.;
&"3
*
80%
6
n-C8H17
Tetrahedron Lett., 1992, 33, 2571.
MQ ,Me 1. 18O"C, 10 h 2. TBAF-DMF
Ph 68%
Me
hire ~~
(85:15
cis-4,5:trans-4,5)
Stork.; Chan, T.Y.; Breault, G.A. J. Am. Chem. SOC., 1992, 114, 7578. BusSnH , Pd(PPh3)4
45%
$Sn% (3654 E:Z)
Mivake.; Yamamura, K. Chem. Lett., 1992,473. REVIEWS: "Ketene Dithioacetals in Organic Synlhesis: Recent Developments" Synthesis, 1990, 171. "Acyclic Stereocontrol via [2,3]-Wittig Sigmatropic Rearrangement" Mikami, K.; Nakai, T. Synthesis, 1991, 594.
SECTION 210:
ALKENES FROM MISCELLANEOUS COMPOUNDS N2
Ph
,OMe P'OMe 0
FVP (350°C) 1
0
-
5
~
*~
P h 4 ~
60%
Tomioka.;Watanabe, M.; Kobayashi, N.; Hirai, K. Tetrahedron Lett., 1990, 31,5061.
Section 210
Alkenes from Miscellaneous
TyM &f) *
+
265
&,) 1111
N
R = AC
(7.3 36.4:l cis anti:cis syn
R = CH2OH
1) 98% 1.7:1 exomdo
1.9) 91% 1:1.3 exomdo
(1
13.2:1 cis antkcis syn
Masjededizadeh, M.R.; Dannecker-Doerig, I.; Little. R.D, J. Org. Chem., 1990, 55, 2742. CloHBNa, THF
76%
/
n-CRH17
n-CRH17
Beels, C.M.D.; Coleman, M.J.;
SynLetr, 1990, 479.
Crearv.;Wang, Y-X.;Gill, W. Tetrahedron Lett., 1991, 32, 729.
")-., a
1 . 2 eq. PhzCHLi , THF HMPA
-
Fe(CO),
2. TFA , -78"C, 1 h 3. aq. NaHCO3
fl:h 67%
Donaldson. W.A.; Hossain, M.A. Tetrahedron Lett., 1992, 33, 4107.
0
F iPr-Ph
OH t-Bu
Ph3COTftMeCN 2,6-lutidine 60°C
6* t-Bu
I)enmark.; Chen, C-T. J. Am. Chem. Soc., 1992, 114, 10674. BnCu(CN)ZnI
THF ,0°C
c
b 9 9 % ee , S)
)---SLPh
m. M-C.P.; Tau, S-I. J. Chem. SOC., Chem. Commun., 1992, 13.
68%
60%
266
Compendium of Organic Synthetic Methods, Vo18
n-C11H23
Pho2SY Li
ClCHzMgCl , THF -78OC --t RT
*
DeLima, C.; Iulla.;Verpeaux, J-N. SynLett, 1992, 133. REVIEWS:
"Methods for the Synthesis of Ally1 Silanes" 1101.
L a d s x J X Synthesis, 1990, 969,
Phosphonates in Organic Synthesis" . . "Vinyl Mmaml..; Motoyoshiya, J. Synlhesis, 1992, 333.
Section 210
bn-C11H23
82%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
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 mines 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 NO ADDITIONAL EXAMPLES
SECTION 212: OXIDES FROM ACID DERIVATIVES 1. NazS03, NaHC03
Hz0.75OC
*
2. ClCHzCOOH , 19 h aq. NaOH , reflux
Brpwn. R.W.J. Org. Chem., 1991, 56, 4974.
SECTION 213: OXIDES FROM ALCOHOLS AND THIOLS
Park, Y.J.;Shin, H.H.; Kim, Y.H. Chern. Left., 1992, 1483.
SECTION 214: OXIDES FROM ALDEHYDES
%CHO
MeNHOH , Z " C
*
0.0 0 E N M~
good yield
Ciganek. E, J. Org. Chem., 1990, 5.5, 3007. 1. Ph2PH , NbCls ,CHzCI;!
Ph
-78°C Ph-P,' Ph 2. BF3.OEt2, -78°C + RT Suzuki.;Hashimoto, T.; Maeta, H.; Matsumoto, T. SynLett, 1992, 125.
ph/\/CHo
6
92%
268
Compendium of Organic Synthetic Methods, Vo18
SECTION 215:
Section 217
OXIDES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 216: OXIDES FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 217: OXIDES FROM AMINES NH,
1. (Et0)2POCI , ether 2. isolate phosphorimidale 3. CH2C12,26 h 5 eq. isoamyl nitrite
-
0
o. b;
OEt
0^,,OEt
Nikolaides, N.; Tetrahedron Leti., 1990, 3I, 1113. Luo, J.; Ganem. B, Tetrahedron Lett., 1991, 32, 3145 [with (Bn02)POHI.
-
H z q , MeOH Na~W04QH20
NI
H
M % s I
0 0
89%
Murahashi. S-IA;Mibui, H.; Shiota, T.; Tsuda,T.; Watanabe, S. J. Org. Chetn., 1990, 55, 1736.
phn
NHMe
acetone ,0°C
-
Murrav. R.W,; Singh, M.J. Org. Chem., 1990, 55, 2954.
Me -.f N@ : rn 00
0""'(yNO'-% HOF , MeCN -10°C
Rozen., Kol, M.J. Org. Chern., 1992, 57, 1342. N- OH
1. urea-HzQ complex ,MeCN
TFAA , 0°C , 3 h
2. Na2HP04, MeCN
rNo
Ballini, R.; Marcantoni, E.; Petrini. M, Tetrahedron Lett., 1992, 33,4835.
70%
Section 2 19
Oxides from Ethers
Qlah.;Ramaiah, P.;Lee,G.K.;
269
SynLetr, 1992, 337.
SECTION 218: OXIDES FROM ESTERS NO ADDlTIONAL EXAMPLES
SECTION 219:
OXIDES FROM ETHERS, EPOXIDES AND THIOETHERS HP(=O)[OH]2, AczO
dioxane ,reflux 2h Klosinski. P, Tetrahedron Lett., 1990, 31, 2025.
Ph‘
’+
0 H
0.1 TeOz , 0.01 HCl Hz02.2 h
74%
0 Ph”V
92%
Kim.;Hwang, H.J.; Cheong, C.S.; Hahn, C.S. Tetrahedron Lett., 1990, 31, 2893.
mY.: Inazu, T. Tetrahedron Lett., 1990, 31, 5955. Ph, s/\
aq. HNO3 ,6h
t
9
0
92% GasDarrini. F.; Giovannoli, M.; Misiti, D.; Natile, G.; Palrnieri, G. J. Org. Chem.. 1990, 55, 1323. Me3PhNBr, Py , H 2 0 , 3 h
t
10°C - RT RBbai, J.; Kapovits, I.; Tanks, B.; Tamas, J. Synthesis, 1990, 847.
270
Section 219
Compendium of Organic Synthetic Methods, Vo18
30% H202, Me
Drabowicz, J.; tyfwa, P.; Popielarczyk, M.; Mikotajczyk, M. Synthesis, 2990, 937. RUCIz(PPh&, PhH
PhS02Cl
Sph
+ , 140°C. 24 h
+P
SO2Ph
h
S
y SPh
c1
54%
71%
Kamigata. N; Ishii, K.; Ohlsuka, T.; Matsuyama, H. Bull. Chem. SOC. fpn., 1991, 64, 3479.
Ph-S-Me
oxone , “wet“ kaolin
-
PhS0,Me 97% C H 9 2 ,reflux , 4 h Hirano, M.; Tomaru, J.; Morimoio, T. Bull. Chem. SOC. Jpn., 1991, 64, 3752. Hirano, M.; Tomaru, J.; Morimoto. T. Chem. Lett., 1991, 523 [with montmorillonite]. Mortierella isabellina (ATCC 42613)
PhA
S‘ Ph
PhA;‘Ph 0
+
48%
(58%ee , R) Holland, H.L.; Rand, C.G.; Viski, P.; Brown, F.M. Can. J. Chem., 2991, 69, 1989.
Ph‘
’V
Bu(MnO&, MeCN
Ph
reflux, 4 h
c
0 Ph”VPh
88%
Firouzabadi. H.; Seddighi, M. Synth. Commun., 1991, 21, 211.
Ph‘
s’Me
Ph-1=0 , 0.1 PhSeOzH 45”C, 1 h
8:
0 Ph‘”Me
86%
Roh, K.R.; Kim, K.S.;Kim. Y . 9 Tetrahedron Left., 1991, 32, 793.
Me’
s*To1
Ti(OiPr)4, t-BuOOH
,H20,45h
Komatsu, N.; Nishibayashi, Y.;Sugita, T.;
0 Me’’.Tol
88%
(73% ee , R) Terrahedron Lett., 1992, 33, 5391.
Oxides from Ethers
Section 219
Ph-
s. Me
1% O s 0 4 , NMO
27 1
*
Katdor.;Hammond, M.Tetrahedron Left., 1991, 32, 5043.
Ph-S-Ph
H ~ I 0 6 - R u 0 4 , 3h CCI@leCN/H20
Ph-SO,-Ph
Ic
76%
Rodriguez, C.M.; Ode, J.M.; Palazbn, J.M.; Martin. V.S. Tetrahedron, 1992,48, 3571.
Ph’
s*Me
3% Mn (salen) derivative HOOH , MeOH
Ph’S-Me
90%
(47% ee , S) Tefrahedron Left., 1992, 33, 71 11.
Palucki, M.; Hanson, P.;
Ph-S-Ph
0
b
NaOBr ,hexaneEtOAc “wet”monimorillonite 15 min *
0 Ph”*ph
78%
Hirano, M.; Kudo, H.; Morimoto. T.Bull. Chem. SOC. Jpn., 1992, 65, 1744.
CC4,4h
Me
Tol’
0 0. To14 s ’ ~ e 95%
*
Me,,Me
(>95% ee , S)
Me
Davis. F.A.; Reddy, R.T.; Han, W.; Carroll, P.J. J. Am. Chem. Soc., 1992, 114, 1428.
Ph-
S-
PhIO , HC1-silica gel “pulverization“
Ph
Sohmiya, H.; Kimura, T.; Fujita, M.;
Ph’
.’
b
Chem. Leff.,1992, 891.
1 eq. oxone, A1203
Me
CH2C12,reflux
PhAS02Cl
c.
3 eq. of oxone led to the sulfone Greenhakh. R.P, SynLetf, 1992, 235.
0 Ph‘S-Me
96%
98%
Compendium of Organic Synthetic Methods, Vo18
272
Section 22 1
REVIEWS:
"Some Routes to Chiral Sulfoxides with Very High Enantiomeric Excesses" Kagan, H.B.; Reviere, F. SynLetl, 1990, 643.
"-
SECTION 220: OXIDES FROM HALIDES AND SULFONATES 1. P(OEt)3, 13OOC 2. Me3SiC1, KI
Ph-C1
OH P' OH
MeCN,6O0C n v 3. H z 0 , RT , 5 min 87% Pilarski, B.; Johnson, J.W. Org. Prep. Proceed. ht.,1990, 22, 209.
;-
TosSOzNa , aq. DMF , 3 min
PhCHzC1 Biswas. G.K.; Jash, S.S.; W PhCHzCl
. . y&runJ.;
c
)))))I)
PhCH2SO2Tol
85%
charvya. P, Id.J. Chem.. 1990, 298, 491.
PhSOzNa , A1203
*
PhCH2SOzPh
>>)))>>) Ben Alloum, A. Synrh. Commun.. 1990, 20, 925.
97%
SECTION 221: OXIDES FROM HYDRIDES
9 c1 PC13 , AICI3, 16 h CHzC12, reflux
PL
c1
-
64%
Dlah. G.A,; Farooq, 0.;Wang, Q.; Wu, A. J. Org. Chem., 1990, 55, 1224.
(0:m:p 44:3:53) Suzuki. €1.; Murashima, T.; Shimizu, K.; Tsukamoto, K. Chem. Letl., 1991, 817. Suzuki. H,; Murashima, T.; Shimizu, K.; Tsukamoto, K. J. Chem. Soc., Chem. Commun., 1991, 1049.
Section 225
213
Oxides from Miscellaneous
SECTION 222: OXIDES FROM KETONES S
1. mCPBA
Ph -(I
-50°C
S' 0
H
65%
(90%E) Barbaro, G.; Battaglia, A.; Giorgianni, P.; Bonini, B.F.; -a Chem., 1990, 55, 3744.
ni. G,; Zani, P. J. Org.
0)
(100
quant.
with MeC(=S)SBu - obtain 80:20 mixture Le Nocher, A.M.; Metzner, P. Tetrahedron Left., 1991, 32, 747.
SECTION 223: OXIDES FROM NITRILES NO ADDITIONAL EXAMPLES
SECTION 224: OXIDES FROM ALKENES NO ADDITIONAL EXAMPLES
SECTION 225: OXIDES FROM MISCELLANEOUS COMPOUNDS This section includes oxides prepared from other oxides
SOZPh S02Ph
1. Br(CH2)3COzR, hv 2. Bu3SnHI AIBN
*
R = thiohydroxamic acid
Padwa;Murphree, S.S.; Yeske, P.E. Tetrahedron Lett., 0
2
H-K'OMe
Ph
Ph
OMe
,PhH
Cu(acac)z
0
SO2Ph 82%
1990, 31, 2983,
0 phyP-OMe
52%
Ph OMe
m v . A . K ; Polezhaeva, N.A.; Mustaphin, A.H.; Khotinen, A.V.; Arbuzov, B.A. Synthesis, 1990, 515.
274
Compendium of Organic Synthetic Methods, Vo18
Section 225
5) 97)
R=Me (95 R = Ph (3 J. Org. Chem.. 1990, 55, 3464.
Chang, 2-Y.;
dco2Me c
1. BuLi
3 C 0 2 M e
2. Me1
8 2
b*
Chou.; Tsai, C-Y.; Huang, L-J. J. Org. Chem., 2990, 55, 5410. 1.3 eq. UDP , PhMe 2.MeI
c) S O2
67%
‘s- 0 2
*
96% 79%
92%
UDP = ultrasonically dispersed potassium Chou. T-S; Hung, S-H.; Peng, M-L.; Lee, S-J. Tetrahedron Lett., 1991, 32, 3551.
0 .Me
i:
OOPS. Me
HO
M~
2. PhMgBr , 5 h
-70°C4 RT
Ph
0 * Me”*Ph **,
Tetrahedron Lett., 1991, 32, 5885.
Benson, S.C.;
Ph-
1. AlMe3 ,RT ,CH2C12 30 min
Bu N+S02C1
(>99%ee)
71%
AlC13, 90°C. 14 h
Katritzkv. A.R.; Wu,J.; Rachwal, S.;Rachwal, B.; Macomber, D.W.; Smith, T.P. Org. Prep. Proceed. lnt., 1992, 24, 463.
S02F Fee. L; Sullivan, E.L.;
BuLi , THF -78OC
-
G S 0 2 - B u 92%
Cusak, K.P.; Funaro, J.M. J. Org. Chem., 1992, 57, 697.
Section 225
Oxides from Miscellaneous
&-
275
0
BuMgBr , THF ,-70°C
c
Tole
Br
81%
Bu
(99% ee , S) Cardellicchio, C.; Fiandanese, V.; Naso. F,; Scilimati, A. Tetrahedron Lett., 1992, 33, 5121.
Falck.;Yu, J. Tetrahedron Lett., 1992, 33, 6723.
'C+J
N-OH
- y j
1. NaBH3CN. pH 3-4
2. PhMe ,reflux
00
94%
Fox, M.E.; Holmes.; Forbes, I.T.; Thompson, M. Tetrahedron Lett., 1992, 33. 7421. REVIEWS:
"AsymmetricCarbon-Carbon Bond Formation Using Sulfoxide-StabilizedCarbanions"
lUkAJ, Tetrahedron Asymmetry, 1992, 3,961. "Cyclic Sulfites and Cyclic Sulfates"
LQLUIY.B.B. Synthesis, 2992, 1035.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
16
PREPARATION OF DIFUNCTIONAL COMPOUNDS
SECTION 300: ALKYNE
- ALKYNE
82%
Stracker, E.C.;
Tetrahedron Lett., 1990, 31, 6815. I . CuC12.2 H2O
Ph- CE C-H
60%
Ph-CEC-CEC-Ph
2. "solidslate" , RT , 3 h
A solid-state Glaser reaction Toda. F,; Tokumaru, Y. Chern. Left., 1990, 987.
f
o'
c:C' H
cat. CuI , 2 TMEDA 0 2 , a ~ e t o n el, h
t-Bu,
0-C ~ C - CC. E 0-t-Bu
77%
Valenii, E.; Pericas. M.A.; Serratosa, F. .I. Am. Chem. Soc., 1990, 112, 7405. 2 q . Ph-CrC-Li
1. CuCN t
2. BuCd-I-Ph+ OTsTIIF, - 7 O T -+ RT
Ph-CZC-CEC-BU
+
Bu-CiC-CiC-BU
71%
8%
UT.; Tanaka, T.; Tanipuchi.;Stang, P.J. .I. Chem. Soc., Perkin Trans. I, 1991, 2892.
.
1. CuBr P v . DBU
Brandsma.;Verkruijsse, H.D.; Walda, B. Synth. Commun., 1991, 21, 137
Alkyne - Alcohol
Section 302
PhCK-H , CUI PdC12(PPh3)2
Ph- CI C-I
277
Ph- CEC- Cz C-Ph
HN(iPr)z, THF
quant.
Witvak. J,; Chan, J.B. Synth. Commun., 1991, 21, 977.
R-c:
cJ1
J3-c: c-
CO2Me
H-CGCJ
Cul ,DMF ,N&03,16 h * Bu~NCI , -20°C+>20°C
C,. 78%
Jeffery, T.; Gueugnot, S . ; Linstrumelle, G. Tetrahedron Lett., 1992, 33, 5757.
SECTION 301: ALKYNE
- ACID DERIVATIVES
NO ADDITIONAL EXAMPLES
SECTION 302: ALKYNE
- ALCOHOL, THIOL
SiMe,
BuLi ,THF
O O *"
c!
/
-78°C
Me3Si ' Tetrahedron Lett., 1990. 31, 7353.
Tomooka, K.; Watanabe, M.;
(6.6
TolO$Y
Ph
N, ,N- S02Tol
1. Ph,SnCH*C=CH, CHzCIz 2. iPrCH0, -78°C. 2.5 h
OH
P
64%
1)
Suzuki, M.; Morita, Y.; Novori. R.J. Org. Chem., 1990, 55,441.
'h%&
H
c: C-H
(94% ee , R)
i3r
92%
76%
Corev. E.J.; Yu, C-M.; Lee, D-H. J. Am. Chem. Sac., 1990, 112, 878.
PhCHO
(Ph-C=C-)zZn, 14 h hexane - THF
Ph
)- C: C- Ph
Bu2PH Me
Niwa, S.;
c
Ph
HO
J. Chem. Sac., Perkin Trans. I. 1990, 937.
(34% ee)
99%
278
Compendium of Organic Synthetic Methods, Vol8
0 +Me
n-C6H,gCZC-Li
*THF
~ z - C ~,H C ,S C
c
8%Me3Ga, R T , 1 h only 3% yield without Me3Ga
Section 302
87%
Me
Fukuda,Y.; Matsubara.; Lambert, C.; Shiragami, H.; Nanko, T.; Bull. Chem. SOC.Jpn., 1991, 64, 1810.
; Nozaki, H.
1 . PhCHO , THF 2. ICH2ZnI
Ph
95%
Tetrahedron Lett., 1991, 32, 1855.
Rozema, M.J.;
Sn(OTf)z, CH2C12
Ph-C:C-H
Ph- CE C
20 : 1) Jefford. C.W.; Tang, Q.; Boukouvalas, J. Tetrahedron Lett., 1990, 31, 995. 1. TFAA
c-
OSiMe3
2.
=(ph
CO,H
, -4O"C, 3h
65%
(>95% ee , S )
Michelon, F.; Pouilhbs, A.; Bac, N.V.; b e l o i s . N. Tetrahedron Lett., 1992, 33, 1743. Br
1.
M
~
~
C
O c-~
E H ~o
Zn, DMF, 70°C. 2 h 2. HCl , 100°C, 1 h Schick.;Ludwig, R. Synthesis, 1992, 369.
o C T M e 0
Also via: Section 360 (Ketone - Ester).
SECTION 321: CARBOXYLIC ACID
- NITRILE
NO ADDITIONAL EXAMPLES Also via:
Section 361 (Nitrile - Ester).
41%
294
\
- ALKENE
-
SECTION 322: CARBOXYLIC ACID
Me-
on 323
Compendium of Organic Synthetic Methods, Vol8
& . 2 eq. LiNEtz 2.0.5 q.12
CO2H
3. hot
62% Tefrahedron,1991, 47, 1997.
Aurell, M.J.; Gil, S.; Parra, M.; Tortajada, A.;
.
1. Mg THF
2. C@
'C02H
HO2C-
with 1. Ba ,THF 2. C 0 2
+
T
C
z
(99
C1)
99%
(2
98)
82%
H
SynLetr, 1992, 593.
Yanagisawa, A.; Yasue, K.;
Section 349 ( h i d e - Alkene). Section 376 (Nitrile - Alkene).
Also via: Section 313 (Alcohol - Carboxylic Acids).
Section 362 (Ester - Alkene).
Mem
SECTION 323: ALCOHOL, THIOL
- ALCOHOL, THIOL
+
Pseudornonas putidt39D Me&H
& OOH
Deluca, M.E.; Hudlickv. T. Tetrahedron Lett., 1990, 31, 13.
"0H
O
Pd(PPh3h , (Me3Sn)z dioxane , sealed lube 1O0-1O5"C124h
*
/
OH
80%
"0H
OH
Kellv. T.R.; Li, Q.; Bhushan, V. Tetrahedron Lett., 1990, 31, 161.
OH
n-C3H7 air , cat. AIBN
ether
89% (=2:1 cis:trans) Kgnai.;Ttimtiskozi, I TetrahedronLett., 1990, 31, 403.
Alcohol - Alcohol
Section 323
295
Hovorka, M.; GunterovB, J.; ZAvada, J. Tetrahedron Lett., 1990, 31,413. 5 9. NaN3 , RT OH W&1. aq. MeOH Me,Si&OH
Me3Si, 0
“%OH
NaN3 in hot DMF gave azido-allylic alcohols
90%
N3
Chakrabortv. T.K,; Reddy, G.V. Tetrahedron Lett.. 1990, 31, 1335.
OH H O A P h
a 0 4
Ph
86%
(47%ee, S) Tomioka. K,; Nakajima, M.;Koga, K. TerrahedronLett., 1990, 31, 1741. Ph
dihydroquinidine pchlorobenzoate OS04,K3Fe(CN)6 KzCO3, aq. r-BuOH
ph-
ooc
Ph
73% improved ee over NMO
Kwong, H-L.; Sorato, C.; Ogino, Y.; Chen, H.;
Tetrahedron Lett., 1990, 31,
2999.
dihydroquinidine
p-chlorobenzoate
p
h
6 Ph
polymer
*
1% 0~04 NMO , 10°C 2-3 d
P h q p h OH
81-87% (85-93% e)
Kim, B.M.; Shagless. K.B. Tetrahedron Lett., 1990, 31, 3003. MgI2, PhH ,AIBN Bu3SnH (added by
syringe pump)
OH
&OH
)-
53%
Me .. Bonlnl.; Di Fahio, R.; Mecozzi, S.; Right, G . Tetrahedron Lett., 1990, 31, 5369.
296
Compendium of Organic Synthetic Methods, Vol8
1. r-BuLi , ether -78OC
2. PhHCO
Me
Section 323
FH Ph80%
Me
Sengupta, S.; Snieckus. V, Tetrahedron Lett., 1990, 31, 4261.
99
HO B u o
Ph/VINMe, Me c1)
98%
Taniguchi, M.; Fujii, H.; Oshima, K.; Utirnoto, K. Tetrahedron Lett., 1992, 33, 4353. piperidine ,AIC13 , 1 h
DCE , 2 5 T
w
H
Lesirnple, P.; J&g. D . C L Synthesis, 1991, 306.
o
q
N
s
91%
Compendium of Organic Synthetic Methods, Vol 8
308
, OMe
dNJ Y
Section 325
OMe BnCHO ,CHzCl2 R T , 15 h
-"II"
~~C~~(THF)~IZ[Z~~CI~I
/
CHO
OH
HO
73%
(80:20 syn:anti) (77*)
Annunziata, R.; Cinauini. M.; m z i . F.; Giaroni, P. Tetrahedron Asymmetry, 1990, 1, 355. P h C O a , PhMe
O2N
02Ny-Jo
c
reflux
B z O A OH
92%
Schmidhauser.;Longley, K.L. Tetrahedron Lett., 1991, 32, 7155. CHO
NHCbz
1. 1 . 1 q.VC13(THP)3 0.6 Zn
2. 1 M HCI
Org. Chem., 1992. 57, 28.
Konradi, A.W.; -..I.
W' h0
0
n
1 . 2 eq. S m 4 , TF
A
CF,
0
Collin, J.; Namy,J.L.; Jones, G.; 0
0
MeA1C12. 0°C hexmdCH2C 12 H v N M e 2 2h
53%
CF,
Tetrahedron Lett., 1992, 33, 2913.
Me OH() € f NMe, ' v i-
Me
":? Me 0
Me
NM%
Me
(97
3)
66%
Fujii, H.; Taniguchi, M.; Oshima. K,; ytimoto. Ic, Tetrahedron Lett., 1992, 33, 4519. 1 . 2 eq. MeZNCHO Na , 8 0 ° C , 5 h
Ph
Ph
OH
Botteghi, C.; Gotta, S.; Marcheti, M.; Melloni. G. Tetrahedron Lett., 1992. 33, 5601.
Alcohol - Amine
Section 326
O H N.C02Ph C 5
Sd2
309
$q-C02Ph
+
OSiMe;?t-Bu
OSiMe2t-Bu 25%
Baldwin.;Turner, S.C.M.; Moloney, M.G.Tetrahedron Lett., 1992, 33, 1517.
I/
NaBH4, EtOH , 0°C pH = 8-10
9>(cH2)S 0 0
9v(cH,), 0 OH
f/
OH 0
36%
30%
Moeller. K.D; Hanau, CE.Tetrahedron Lett., 1992, 33,6041. 1. n-C3H7NH2
*
2. MeOH ,reflux
CO,Et
P
+ 91(cHz)S
N
Amri, H.; El Gaied, M.M.; Ben Ayed, T.; Villeras, J. Tetrahedron Lett., 1992, 33, 6159.
0
ZnBr , THF ,25”C
0
/Jul NHPh
c
bw OH 0
NHPh 91%
Taniguchi, M.; Qshima. K.; Utimoto. K. Chem. Lett., 1992, 2135.
SECTION 326: ALCOHOL, THIOL OH
PhCH2NH2, Zn ,2h NaBH3CN, n-PrOH H2O , reflux
OMe Bernoas. R.C, Tetrahedron Lett., 1990, 31, 469.
HO 1. BuCu
MeHN
- AMINE *
NHBn 82%
,;IoH
. ; LiAIH4 Ph’”
1. BuZnI
HO L
SPh 2. LiAlH4 MeHN 3.Hz.W-C 3. H2, Pd-C Me Couty, F.; Darm, J-C.; Prince, B.; Puchot, C. Telrahedron Len., 1990, 31, 2889.
s;
Section 326
Compendium of Organic Synthetic Methods, Vol8
310
0
e- ,NaOMe ,MeOH Bu4NHS04,15"C Mex=
0
Me
C02H
M~
graphite electrodes 500 m A ,80 h
OH
3.9 v
Me
75% Fasseur, D.; &~Q,&B.; Cauliez. P.; Debacker. M.; Couturier, D. Tetrahedron Lett., 1990, 31, 1713.
Bn
Nq-+
H
Boc.
OH
H
N
H
6)
(1
=
OH 65%
Vara Prasad, J.V.N.; Rich. H. Tetrahedron Left., 1990, 31, 1803.
Me. t-BUN
N
/I
A
1.1-BuLi ,THF -78°C
php +J
Ho
2. PhCHO , -5"; t-BuN 60% Solladik-Cavallo,A,; Bencheqroun, M. Tetrahedron Lett., 1990, 31, 2157. 1. BuLi ,ether 2. MeOMs
N.
3. Y O ; aq. HCI
Me
QyN.
* 0
Simig, G.;Schlosser. M. Tetrahedron Lett., 1990, 31, 3125.
Me
Me
67%
M o ( C O ) ~reflux , H20/MeCN
Me'ph% N*O
MeHN
n-C4H9 2-3 h
OH
78%
Cicchi, S . ; Goti, A; B u n'L L;Guama, A.; De Sarlo, F. Tetrahedron Lett., 1990, 31, 3351.
(73
Mlkami.; Kaneko, M.; Loh, T-P.; Terada, M.;
27)
59%
Tetrahedron Lett., 1990, 31, 3909.
31 1
Alcohol - Amine
Section 326
0 Chini, M.; Crotti. P.;
a
BnNH2, LiC104 MeCN.64h
F
H NHBn
80% Tetrahedron Lett., 1990, 31, 4661.
'
1. Dibal , CHzC12 , -78°C 2. PhMgBr ,ether
Ph
3. aq. NaHC03
Ph
bH
5. H3O+
69%
Polt. It,;Peterson, M.A. Tetrahedron Lett., 1990, 31, 4985.
N3 OH
NaN, , LiCIO, MeCN ,80T
n-c6H 13
24 h
+ +
n-C6H13
HO n-C6H13
N,
92.5) 96%
(7.5
Chini, M.; Crotti. P,; Macchia, F. Tetrahedron Lett., 1990, 31, 5641. Rh2(OAc)4, PhH
o N f M e /
reflux95h
N Me
do Me
OH
Me
77%
Etkin, N.; Babu, S.D.; Fooks, C.J.; Durst...I.Org. Chem., 1990, 55. 1093.
1. BuLi
3. NaBH4, THFEtOH \
NMe2
H
47% overall
Katritzkv. A.R, ; Lue, P.; Chen, Y-X. J . Org. Chem., 1990, 55, 3688.
Re
HSiMezPh , CHzClz, 25°C CsF , 18-cfown-6,9h
0 ; . u~ -
67%
OSiMe,Ph
Rubina, K.; Shymanska, M.; Lukevics, E. Synth. Commun., 1990, 20, 2439.
Compendium of Organic Synthetic Methods, Vo18
312
2 eq.Sml2 ,ethylene glycol HMPA , RT c
N-OBn 4
Ph
Ph
Section 326
d N H O B n 83%
Tetrahedron Lett., 1991, 32, 3555.
Hanamoto, T.;
0
H
.MeCN
Ph 10 kbar , 2 4 h
H
15% at atmospheric preessure Potsuki. K; Nishiuchi, M.; Kobayashi, S.; Nishizawa, H. J. Org. Chem., 1990, 55, 2969. 1. BuLi , ClSiMezH, ether 2. P ~ [ ( C H ~ = C H ~ ) M ~ ~ S ~ I ~ O ) Z 0.2%.RT , 3 0 rmn
NH2
3. EDTA-2 M a , RT * 4.30% H 2 0 2 , KF KHC03 MeOH , THF ,RT I
ph$t
77%
(80:20 syn:anti)
Nakagawa, Y.; Iray,J. Org. Chem., 1990, 55, 3438.
;
OH NHBoc
1.0.5 [V2C13(THF)&
1 h addition of aminoaldehyde 2. 10%aq. Na tartrate
Konradi, A.W.;
&ma J. Org. Chem., 1990, 55, 4506. OH
P h / t Ph OH
Wt.; Ahuja, J.R. J.
1. soc12 ,cc14
2.UN3, DMF , 12OOC * 3. H2, Pd-C
OH
OH Ph &Ph
81%
NH,
(196% ee , RS)
Chem. SOC., Chem. Commun., 1991, 95.
porcine pancreatic lipase EtOAc
k
70%
(>201 dr)
c,
Q Ac
OH
+
( T O H H
(-) ,92%ee , S (9%) (+) ,90%ee , R (90%)
Asensio, G.; Andreu, C.; Marco, J.A. Tetrahedron Lett., 1991, 32, 4197.
Alcohol - Amine
Section 326
PhCHO
'*
TolSOzCH2CN , I % AgOTf 25"C, CH2Cl2 Me
Me
313
OH PhL N H M e
me 96% (83% ee)
PPhz
2. LiAIH4, THF
Sawamura, M.; Hamashima, H.; Ito. Y . J . Org. Chem., 1990, 55, 5935
0 %Me,
@ Me
MeCN t
hv (near UV)
quant.
\
quantum efficiency = 0.56
m; Cao, Q. Tetrahedron Lett., 1991, 32, 3915.
(93
Canas, M.; Poch, M.; Verdageur, X.; Moyano, A.; &j&.&A, 1991, 32, 6931.
OH M e A O H
H' N'CHPh,
7)
96%
Tetrahedron Lett.,
;
1.1 MsCl, 3 NEt3 CHzC12
0°C (8 h); RT (36 h)
Me
CHPh2
77 %
Poch, M.; Verdaguer, X.; Moyano, A.; PericBs, M.A.; Riera, A. Tetrahedron Lett., 1991, 32, 6935.
c
Me02C"'no N
0
1. Phy N=O 2.0~04,NMO
HO,
OH
3. Hz , Pd-C
Defoin. A,; Pires, J.; Streith, J. SynLett, 1991, 417.
H
3 14
Compendium of Organic Synthetic Methods, Vol8
G-
Me
Section 326
1. BF3*OEt2 2. sec-BuLi , THF ,-78OC
3. PhCHO ; 5% HCI
79%
Kessar. S .V,; Singh, P.; Vohra, R.; Kaur, N.P.; Singh, K.N.J. Chem. Soc., Chem. Cornmun., 1991, 568.
A N' Ph \
ph%
Me
.
1. PhCHO h w i s acid 2. Na , iPrOH. THF O°C --f RT 3 . 4 N HCI , THF , 60°C 4.3NKOH, 1 h
QIH2 OH
NH2 OH i-P h v P h
Ph+Ph Me
Me
(39
61)
94%
Barluenea.; Joglar, J.; Gonz&lez, F.J.; Fustero, S.; Kriiger, C.; Tsay, Y-H. Synthesis, 1991, 387.
0;;
0'
MqSiN, , L-(+)-DIPT 10% TiCh(0iPr)z -10°C , 2 0 h
60%
(46% ee)
SynLett, 1991, 774.
Hayashi, M.; Kohrnura, K.; Me3SiN3, THF , 6 d
n-C6H 1 3
cat. Ti(OiPr),
dn-c6H13 OSiMe,
b
N,
Sutowardoyo, K.I.; Emziane, M.; Lhoste, P.;
(92
+ 8)
74%
Tetrahedron, 1991, 47, 1435.
5
C02t-BU n-C6H 13
~-C&I~CHO CH2Cl2 ,
P~C=N-CH~CO~~-BU
89%
OH
(43% dr)
Gasparski, C.M.; Miller. M.J. Tetrahedron, 1991, 47, 5367. NaN3, NH4CI aq. MeOH ,25"C
OH
60 h
w M e 3 X
HO
(3
OH
+
Chakrabortv.;Reddy, G.V. Tetrahedron Lett., 1991, 32, 679.
"XH N3 O H 1)
88%
315
Alcohol - Amine
Section 326
Q
"W%
M.~
NHOMe
.OMe
e- , Sn cathode, C anode = 5% C , iPrOH , EbOTs
Shono. T,; Kise, N.; Fujimoto, T. Tetrahedron Lett., 1991, 32, 525. Shono. T.; Kise, N.; Kunimi, N.; Nomura, R. Chem. Lett., 1991, 2191. 1. NMM
Ph
3. NaBH4, H20 -15°C. 30 see Rodriguez, M.; Llinares, M.; Doulut, S.; Heitz, A.; 923.
Ph
Tetrahedron Lett., 1991, 32,
woM
1. LiDBB , THF , -95°C
9 S P h
M e O O C H :
2-
81%
79%
-95"C, 90 & OH LiDBB = lilhium di-t-butylbiphenyl radical anion
Tsunoda.;Fujiwara, K.; Yamamoto, Y.; Ilbs.Tetrahedron Lett., 1991, 32, 1975.
P N
Me
0
Bra
1. NaOMe , PhH , reflux 2. NaBH4
Ph
c1
3. Me02CC1, PhH reflux
0
58%
Me- N C02Me0C02Me
Coates, A.J.; Malone, J.F.; McCarney, M.T.; Stevenson, P.J. Tetrahedron Lett., 2991, 32, 2827. Br OTHP ,
1. Ph+ 0
MeHN-
PPh3f
Br-
Kinder, F.R. Jr.; Jarosinski, M.A.;
2. NaH , THF , heat 3. H+
N I
Me
J. Org. Chem., 1991, 56,6475.
76%
3 16
Compendium of Organic Synthetic Methods, Vol 6
OSjMe2t-Bu
OHC1Me
Section 326
OSiMqt-Bu
1. LiHDMS
* M
2. ally1 MgCi
M
e
+
NH2 (4
. . ; m Giacomini, D.; Mezzina, E.; 1991, 32, 2961.
OSiMqt-Bu
+Me N*2 96)
(82
-nus.
18)
88%
P.; Moursounidis, T. J. Org. Chem., 1991, 56, 1529.
Murakami, M.; Hayashi, M.; =.I.
Ph Me,,
66%
; Zarantonello, P.Tetrahedron Lett.,
Org. Chem., 1992, 57, 193.
1. Dibal , ZnCl2 , THF 2. H 2 0 , OH-
3. LiAIH4, THF
Ph
Ph
*
Ph
3)
(97
92%
Aguilar, E.; w r o . S;. Olano, B.; Viado, A.L. J. Org. Chem., 1992,57, 1219. Bar1ueqga-L ; Aguilar, E.; Olano, B.; Fustero, S. Sydett, 1990, 463.
;-
1. Na(Hg) , aq. MeOH 2. NaOH , aq. EtOH
(96%de)
Martin. S.F.; Hartmann, M.; Josey, J.A. Tetrahedron Lett., 1992, 33, 3583.
HO
Alcohol - Amine
Section 326
OH
1. Dibal 2. NH4Br 3.MeNH2
PhXCN
4.NaBH4
317
OH
t
Ph
A-NHMe
79% Zandbergen, P.; van den Nieuwendijk, A.M.C.H.; Brussee. J,; van der Gen, A.; Kruse, C.G. Tetrahedron, 1992, 48, 3977.
H P
O
8CF3 E t
1. Bn2NH , RT 2. NaBH4, EtOH , RT
- 7:; Bn2N
85%
Ph
Ph
BCgu6, J-P.;Bonnet-Deppon, D.; Sdassi, H. Tetrahedron Lett., 1992, 33, 1879. ral liver microsornes
E~OH,phosphalebuffer
iBz
P h O d o
cj
36°C
c
(86%ee)
Bz
40%
Rao, A.B.; Rao, M.V. Tetrahedron Lett., 1992, 33, 4077.
;
Me,
H
'% NH2
1. BuLi ,THF , -80°C 2. AIMe3, PhMe ,-80°C 3. -80°C -+ 0°C
+
4. NaF, H20
HO
H N,H
Najime, R.; Pilard, S.; Vaultier. M, Tetrahedron Lett., 1992, 33, 5351. 1. BuLi , -5OT 2. r-BuLi , -3O'C -+ 20°C elher, PMDETA
PhHNA
I
3. PhCHO 4. H,O
PhHN
PMDETA = N,N~~".N"-pentamethyldiethylenediamne
Barluenea; Gonzllez, R.; FailanBs, F.J. Tetrahedron Lett., 1992, 33, 7573.
0'
iPrMezSiN3, TMSOTf )3
,O0C,48;
OH
Nupent.J.Am. Chem. SOC., 1992, 114, 2168.
,$t
OSiMe2(iPr)
ON.,
(93% ee)
86%
69%
Section 327
Compendium of Organic Synthetic Methods, Vol8
318
REVIEWS :
"The Synthetic Utility of a-Amino Alkoxides" SynLetl, 1992, 615.
SECTION 327: ALCOHOL, THIOL
- ESTER OH
baker's yeast 20%sucrose
dialysis tube Spiliotis, V.; Papahaatjis, D.; m u s s i s . N, Tetrahedron Lett., 1990, 31, 1615. H20,
nC3H7CHO. I d
SOzN(iPr)z
S02N(iPr)2
70% (42% de)
Baylis-Hillman coupling reaction
Basavaiah.;Gowriswari, V.V.L.; Sarma, P.K.S.;Dharma Rao, P. Tetrahedron kit., 1990, 31, 1621.
OSiMe, Me&
Me
90%
(35 1) Ishikawa, A.; Uchiyama, H.; Katsuki, T.; Yamaguchi, M. Tefrahedron Lect., 1990, 31,2415.
9
cat. OsQ , NMO aq. acetone, RT
C02Me
HO
12h
111
OH
6 " O H CO2Me
85%
Backenstrass, F.; Sueith.;Tschamber, T. Tetrahedron Lett.. 1990, 31. 2139.
HO>
1. BuzSnO , PhMe
Ph reflux , 6 h OH 2. BzCl 3. Me3SiC1
Ph w
Me3Si0 (98
OBz
-t
BzOT(OSiMe3 2)
83%
Reginato, G.; Ricci, A.; Roelens. S,; Scapecchi, S. J. Org. Chem., 1990. 55, 5132.
Alcohol - Ester
Section 327
3 19
YH do -- & OH
porcine pancreatic lipase
o
(n-C3H7C0)Z0
+Y
*
&n-C3H7
n-C3H7
0
O0 n-C3H7 0
1)
(99
Ramaswamy, S.; Morgan, B.; Oehlschlager, A. Tetrahedron Lett., 1990, 31, 3405. ,
A
,
Pseudomom fluorescens
OH OH
lipase
CHCI, 300~
=/OAc
j n + A OAcOH 40%
I
OAcOAc 60%
(>98% ee)
Santaniello, E.; Ferrabuschi, P.; Grisenti, P. Tetrahedron Lett., 1990, 31, 5657. Candida parapsilosis
63%
(>99% R)
Ham, H.; S b i m i u A; Hattori, S.; Yamada, H. J. Org. Chem., 1990, 55, 4377. Ph
wOMe
-
OSiMe2t-Bu PhCHO , TMSCl [CPZYbC112
OSiMe3 Ph\C02Me Ph (82
Gong, L.; Streitwieser. A. J. Org. Chem., 1990, 55, 6235.
+
OSiMe3 Ph+C02Me Ph 18)
70%
Mew0SiMe3 , Sn(0Tf)z PhCHO
*
SEt
Me
'
, Bu$n(OAc)2
E t S T P h Me
85%
(100% syn; >98% ee)
Mukaiyama, T.; Kobayashi, S.; Uchiro, H.; Shiina, I. Chem Lett., 1990, 129. Mukaiyama, T.; Uchiro, H.; Shiina, I.; Kobayashi, S. Chem. Lett., 1990, 1019. Mukaiyama, T.; Shiina, I.; Kobayashi, S . Chem. Lett., 1991, 1901. ;Uchiro, H.; Fujishita, Y.; Shiina, I.; wukaivama. T, J. Am. Chem. Soc., 1991.
113,4247.
320
Compendium of Organic Synthetic Methods, Vo18
immobilized bakers yeast MeOH t
0
) , , CO,Et
Section 327
OH
i./
C02Et 56% (97% ee , S) Naoshima.;Maeda, J.; Munakata, Y.;Nishiyama, T.; Kamezawa, M.; Tachibana, H. .I. Chem. SOC., Chem. Commun., Z990, 964.
.
0 CHzClz
P \ h v '*OH BFyOEt2, (CH20H)y 0 61% 0°C (5 h) + RT (20 h) Nagumo, S.; Matsukuma, A.; Inoue, F.; Yamamoto, T.; Suemune, H.; Sakai. K. J. Chent. SOC., Chem. Commun., 1990, 1538. PhCHo
iPrCHO , 15% SmIz
9
rk0
OH
>99:1 anti:syn) Evans. D.A.; Hoveyda, A.H. J. Am. Chem SOC.,1990, 112, 6447.
e
95%
1. Li , NH3 ,THF
-78"C, 30 sec
72%
C02n-C8H, 72. aq. NH4CI
CO~~-C~HI~
van der B a n . J.L. ; Bamick, J.W.F.K.; Bickelhaupt, F. Synthesis, 1990, 897. OSiMe,t-Bu 20% Z a t z 1 B PhCHO -b
=(OEt
n A C02SiMe2,-Bu
PhMe , -78°C
OSiMqr-Bu * ELo,Cdph (60% ee)
79%
Mukaiyama, T.; Takashima, T.; Kusaka, H.; Shimpuku, T. Cheni. Lett., 1990, 1777.
*
C02Bn
cat. Mn(dpm)z, 02,PhSiH3 0°C , iPrOH
+
OH d c o 2 B n
Mn(dpm)2 = bis(dipivaloy1methanato) manganese (11) Chem. Lett., 1990, 1869. Inoki, S.; Kato, K.; Isayama, S.;
91%
Alcohol - Ester
Section 327
OH
, ! , , C02Me
32 1
OH OH
1. LDA 2. PhCHO
V
OH OH
+
P h CO,Me
W
(30 1. EtGiCl 2. PhCHO , Tic14 (93 Shirai, F.; Gu, J-H.; mi.T.Chem. Lett., 1990, 1931.
M e g ~ , Tic14 c 0
w
Et02C
*
HO~U
Ti02 , CH2C12 , -80°C
h
CO2Et
OH
I I ~
Me
Me
OSiMe3
P
C02Me 70) 86% 7) 75%
Ali, S.M.; hmguXL SynLett, 1990, 391. Ph3SiClO4, 1.5 h CH2C12, -78°C -+ -30°C@0H m
C02Me 95%
C02Me Inokuchi, T.; Kusornoto. M.; Matsurnoto. S.; Okada, H.;
C02Me
SrnI2, THF-HMPA
Hon.;Lu, L.; Chu, k-P. Synrh.
Me02C
t
f-BuOH
Chem. Left., 1991, 2009.
70% Commun., 1991, 21, 1981
(15
85)
Lei, B.; Fallis. A.G. Can. J. Chem., 1991, 69, 1450.
6 0
C12CeCH2C02Et, THF -78°C
5
HO
*
Liu. H-J.; Zhu. B-Y. Can. J. Chem., 1991, 69, 2008.
CO,Et 96%
75%
322
Compendium of Organic Synthetic Methods, Vol 8
Section 327
Trost. B.M.; Granja, J.R. J. Am, Chem. SOC.,1991, 113, 1044.
B , - O q 0
0
2 eq. SmI2, THF , -78OC
Ph
OH
1)
(>200
76%
Molander.; Etter, J.B.; Hatring, L.S.; Thorel, P-J. J. Am. Chem. SOC., 1991, 113, 8036.
t-Bu0,C
-p-k B.O
enolate (98:2)
(1,2: 1,3-dioI)
. . Lupattelli. P.; Bersani, M.T.; Mincione, E. Tetrahedron Left., 1992, 33,6181. Bovlcelh.; . . Bovlcelh.;Mincione, E.; Ortaggi, G . Tetrahedron Lett., 1992, 32, 3719. Ph
\
Tic14 - LiCl ,THF -20°C , 15 min
OH Shimizu, M.; Yoshida, A.;
* Ph\ +ph\
HO
(89 SynLett, 1992, 204.
OH
.-' 1)
OH
96%
Compendium of Organic Synthetic Methods, Vol8
340
*
0
OH
0.5 Br2 ,CH2C12
Br
fl\n-C,H,:. Br
n-C6H 13
(0.7j3.0
Konaklieva, M.I.; Dahl,M.L.;
Section 330
A-C,H13 OH
:
1)
54%
Tetrahedron Lett., 1992, 33, 7093.
SECTION 330: ALCOHOL, THIOL
- KETONE
1. dihydroxy acetone phosphate
OH
fructose-1,&diphosphate aldolase (EC 4.1.2.13) 2. acid phophatase pH 4.8
OHwib in (+)-em-brevicomin
40%
Schultz, M.; Waldmann.; Vogt, W.; Kunz, H. Tetrahedron Lett., 1990, 31, 867. OSiMe3
O
H
C
T SiMq
TBAF ,Si@
C
C
l
Ram6n. D.J.; Yus.
M
2. PhCHO , -78°C -+ + 2 0 T
OH
Ph
3.H20
:
Me
Me
-78OC
M = Li , THF
M = SiMeZl-Bu
BF3*OEt2, CHzClz
18
98
Evans.;Gage, J.R. Tetrahedron Lett., 1990, 31, 6129.
n
0 0
AAX 60%
M.Tetrahedron Lett., 1990, 31, 3763, 3767.
OSiEt,
0
H
n 0 0
OH
60%
kee T.V.; Roden, F.S. Tetrahedron Lett., 1990, 31, 2067.
+
34 1
Alcohol - Ketone
Section 330
\rf\\ 0
PhCHO ,EtzMeSiH PPh2Me , To1 -5T, 2h
0
OSiMeEt, 99%
(83:17
syn:anti)
Matsuda I,; Takahashi, K.; Sato, S. Tetrahedron Lett., 1990, 31, 5331. 1. LDA 2.PhCHOb
+
M~
Me,SiO
OSiMe,
E.,&
-
Me
Me,SiO 90)
(10 (99
with CITi(0iPr)J
Panyachotipun, C.; m r n t on.
Ph
1)
Tetrahedron Len., 1990, 31, 6001. (PhSeh , CH2(C02Me)2
Ph
MeOH , NaC104 Inokuchi, T.; Kusumoto, M.;
70%
J. Org. Chem., 1990, 55, 1548. ECHO , ZnCl2 Cl12C12
-
OSiMe, 61%
Moiseenkov, A.M.; Czeskis, B.A.; Ivanova, N.M.; m o v . O.M. Org. Prep. Proceed. Int., 1990, 22, 215. iPrCHO , CH2C12 TiC14, 3.5 h
* z*
OBz
88% (92% dr)
Trost. B.M, : Urabe, H. J. Org. Chem., 1990, 55, 3982. MoOPD
O
*
a safer alternative to M ~ O P H
P&Ph 0
MoOPD = oxodiperoxymolybdenum (pyridine)-1,3-dimetyl3,4,5,6-tetrahydro-2( 1H)pyrimidinone = MoOy Py-DMPU Anderson, J.C.; Smith, S.C. SynLeft, 1990, 107.
47%
Ph
342
Compendium of Organic Synthetic Methods, Vol 8
,JH4Y
Section 330
TFA ,aq. THF
76%
Stone, G.B.; h h s U L L & J. Org. Chem.. 1990, 55, 4614. 0
1.
PhCHO Sasai, H.; Kirio, Y.;
Br
, WOf-Bu)4 THF , -30°C
P h d 2. MsCl , NEt3 , CH2C12 * -78°C -+ -30°C Br 56% J. Org. Chem., 1990, 55, 5306. ‘
1. ethylene glycol ,TsOH PhH , reflux
0
2. LiAlH4, THF , 0°C
M~O 3. wet silica ~gelC A b
Hitchcock, S.R.; Perron, F.; Martin, V.A.;
HO
2ji
81%
Synthesis, 1990, 1059.
YU
PhCHO
91%
(60%ee)
Mukaiyana, T.; Inubushi, A.; Suda, S.; Hara, R.; Kohayashi, S. Chem. Lett., 1990, 1015.
Dh
,
Dl.
1. Yb ,RT
* n *
Takaki.;Beppu, F.; Tanaka, s.; Tsubaki, Y.; Jintoku, T.;
J. Chem. Soc., Chem.
Commun., 1990, 516.
Ph
icf-
0 Ph
B q S n H , PhH ,hv
30 rnin
b
u Ph
p
h
93%
H w g a w a . E.; Ishiyama, K.; Horaguchi, T.; Shimizu, T. .I. Chem. Soc., Chem. Commun., 1990, 550.
Section 330
PhCHO
Alcohol - Ketone
&:L:CHzCIz, Me
E t S v P h Me
SnO + Me3SiOTf
-t
EtS Me
(94 (91 96 ee)
Me
OSiMe,
0
OSme,
0
-78°C
343
6)
82%
Mukaiyama, T.; Uchiro, H.; Kobayashi, S. Chem. Leu., 1990, 1147.
0 PhA TeBu
1. BuLi
2.
t
PhQB :u
85%
OH Me r-Bu 3. H+ Hiiro, T.; Morita, Y.; Inoue, T.; Kambe. N.; Ogawa, A.; Ryu, I.; Sonoda. N, J. Am. Chem. SOC., 1990, 112, 455.
Me Sn(OT02, NEt3 TiCI4, iPr2NEt
(95
5) 83% 99) 86% Evans.;Clark, J.S.; Mettemich, R.; Novack, V.J.; Sheppard, G.S. J. Am. Chem. SOC., 1990, 112. 866. Evans. D.A.; Rieger, D.L.; Bilodeau, M.T.; Urpl, F. J. Am. Chem. Soc., 1991, 113, 1047.
0"
0
(< 1
25"C, 10 h
2q.
b " a $
SbCf
a:, 88%
Schulz.;Kluge, R.; Siviai, L.; Kamm, B. Tetrahedron, 1990, 46, 2371. 1. PhCHO ,BiCl3 CH2Cl2, RT
Phh0siMe3
b
0
OH
25 min PhU P h 2. MeOH , IN HCI Wada. M.; Takeichi, E.; Matsumoto, T. Bull. Chem. SOC.Jpn., 1991, 64, 990.
94%
344
Section 330
Compendium of Organic Synthetic Methods, Vol 8
SnCL4, CHzClz , -78°C
PhCHO
Q N S
" " P h w
Me
OH 0
L,
P h ' v c
Me
Ph
43%
(6S:35 anti:syn)
o Ph
Chikashita. H. ; Tame, S.; Yamada, S.; Itoh, K. Bull. Chem. SOC.Jpn., 1990, 63, 497. 0
HO
P h 5 Ph 0
hv ,MeCN =
SnBy
Me-Ph
2O0C
(89:ll E:Z)
Ph
Ph +
0
Me 0
32) 89% (68 (89:ll E:Z) Takuwa. A,; Nishigaichi, Y.; Yamaoka, T.; Iichama, K. J. Chem. Soc., Chem. Commun., 1991, 1359.
OSiMe, M e & - ph
1. ot ,cat. Ni(mac)z, DCE
iPrCHO , RT
2. KF , MeOH
Ni(rnac)z = bis-(3-methyl-2,4-pentanedionato)nickel (11)
OH
Ph
75%
Takai, T.; Yrunada, T.; Rhode, 0.;W i v a m a . T, Chem. Left.,1991, 281. Takai, T.; Yamada, T.; Mukaiyama, T. Chem. Lett., 1991, 1499.
4°SiMezr-Bu Me , 10% InCI3 L, u 7 t
PhCHO
ClSiMezi-Bu ,-43°C , 1 .S h
-
B
~ 93%
Me
Mukaiyama, T.; Ohno, T.; Han, J.S.; Kobayashi, S. Cheni. Left.,1991, 949.
MeSSiO Ph&Me
aq. HCIIO ,TIJF Y b(0Tfh
* P h G O H Me
Chem. Lett., 1991, 2087. 1. NaN(TMS)Z, THF , O°C
Ph
)(&
,acetone, -78°C 2 min
Adam.;Prechtl, F. Chem. Ber., 1991, 124, 2369.
Ph .-
Ph
944b
345
Alcohol - Ketone
Section 330
0
Ph
-
Guertin, K.R.;
JL
>X
1. LDA , THF , -78°C
2
Ph &OH
,aceton:
77%
-78"C, 30 min (inverse addition) Tetrahedron Lett., 1991, 32, 715. 1.2-ICr2BH , CDC13 1,5 h , 0°C
0
2.PhCHO 3. H20 2-ICr2BH = di-(2-isocaranyl)borane Boldrini, G.P.; Bortolitti, M.; Tagliavini, E.; Trombini. C,; Umani-Ronchi, A. Tetrahedron Let?., 1991, 32, 1229.
&
J / $
;L . k;iT
OMe
OMe
5 3
66%
(94% ee , R)
Davis. F A ; Kumar, A.; Chen, B-C. J. Org. Chern., 1991, 56, 1143. Davis.;Weismiller, M.C. J. Org. Chern.,1990, 55, 3715. [dimethoxy derivative] 1.2 eq. SmI2
0 2. H30' n-C8H,+ c1
+
n-C H
*
OH 171+n-C,H,, 0
75%
Aryl acid chlorides lead to 1,Zdiketones Collin, J.; Namy,J-L.; Dallemer, F.; Kacan. H.B, J. Org. Chern.,1991, 56, 3118.
OH 0
LDA , THF MgBrz-OEtz
Ph
-70°C-+RT
*
P h g P h i- P h 4 P h Me Me
2) 73% (98 Swiss, K.A.; Choi, W-B.; Liotta. D.C. ; A b d e l - M a; Maryanoff, C.A. J. Org. Chem., 1991, 56, 5978.
346
Section 330
Compendium of Organic Synthetic Methods, Vol8
PCWP = peroxytungsto phosphate
Sakata, Y.; khii. Y.J. Org. Chem., 1991, 56, 6233. e- , Sn cathode
iPrOH , 2 5 T
Me
Me
60% 5% Shono. z; Kise, N,; Fujimoto, T.; Tominagi, N.; Morita, H.J. Org. Chem., 1992, 57, 7175. Shono. T,; Kise, N. Tetrahedron tell., 1990, 31, 1303. Bu3SnSiMe3 BnEt3NCI
&,
~
74%
HO
Br
Mori.; Kaneta, N.: Isono, N.;
Ihmeb, H.; Maggini, M.; Prato.
i. M, Tetrahedron Lea, 1991, 32, 6139.
m, Scorrano, C . Tetrahedron Lett., 1991, 32, 6215.
1. iPrCHO ,CH&& BiC13 , 3 NaI
OSiMe3 2. MeOH ,HCI
0 OH 90% Le Roux, C.; Maravat, M.;Borredon, M.E.; Gaspard-Iloughmane,H.; Qhd Tetrahedron .
Lett., 1992, 33, 1053.
OSiMe-,
0
PhCHO , Gd(OTf),
1:4 (H20:THF), 20 h RT
=-
OH
@Ph (78
mS.: Hachiya, I. Tetrahedron Lett., 1992, 33, 1525.
+
F
P 22)
h 88%
Alcohol - Ketone
Section 330
347
Ph
4OSiMei -c6 min
-CHO
0
c
OSiMe,
[Ru(salen)(NO)(H~O)]' Ph Odenkuk, W.; Whelan, J.; Bosnich. B. Tetrahedron Lett., 1992, 33, 5729. PhI(OzCCF3)z ,TFA , 3 h
0
P h ' v Me
0 Ph J L O H
b
MeCN ,H2O
69%
R.K;Berglund, B.A.; Penmasta, R. Tetrahedron Lett., 1992, 33, 6065. 1.2.2eq. S d z , MeCN
Ph
c1 +
0 PhAMe
2. H30+
c
Ph%H
Me Ph
78%
Ruder. S.M, Tetrahedron Lett., 1992, 33, 2621.
Ikeda, S.; Chatani, N.; Kajikawa, Y.; Ohe, K.; Murai. S. J. Org. Chem., 1992, 57, 2.
(4.2
1)
64%
Motberwell.; Sandham, D.A. Tetrahedron Lett., Z992, 33,6187. OSiMe3
0.5%TiCp~(CF3Cs03)z PhCHO ,CDZCiz 98% ee)
Leanna.;Sowin, T.J.;Morton, H.E. Tetruhedron Lett., 1992, 33, 5029. SECTION 335: ALDEHYDE
- AMINE
H;F/CO,PPh3
CHO
CHO
PPh2 EIOAC
55°C. 22h
PPh2 64%
99:1 exo:endo Kobayashi, S.; Murakami, M.; Harada, T.; Mukaiyama, T. Chem. Let?., 1991. 1341.
374
Compendium of Organic Synthetic Methods, Vol8
-
PhH
-OH
q-@H%M€)2
no oxidation of non-allylic alcohols Yana. H,; Li, B. Synth. Commun., 1991, 21, 1521. DMF , P O c b 0°C + RT,4 h
OMe
bCHo 81%
Cr$$
wMeo MeO"'
CHO
OMe
Tetrahedron Lett., 1991, 32, 3875.
Ramesh, N.G.;
'OzMe
60%
5% Pd(0Ac)z 15% PPh3, 80°C
HO
CHO
W i n . J-M. Tetrahedron Lett., 1991, 32,6113. dC I SN ~ C I, ~
PhCHO
Section 34 1
DCE , HzO ,25"C, 4 h
Ph
, N*
CHO
57% J3morsv. S.S. ; Badawy, D.S.; Nour, M.A.; Peller, A. Tetrahedron Letl., 1991, 32, 5421.
Menicagli. R,; Malanga, C.; Guagnano, V. Tetrahedron Lett., 2992, 33, 2867. SnC12-2 H2O , CH2C12
*
-CHO 94%
Ford, K.L.; Roskamn. E.J, Tetrahedron Left., 1992, 33, 1135.
H- CSC
l
NH2
2 eq. MezPhSiH , CO , PhH Rb(C0)12, 100°C , 2 h
OHC
Matsuda.; Sakakibara,J.; Inoue, H.; Nagashima, H. TefrahedronLett., 1992, 33, 5799.
Amide - Amide
Section 342
x
375
uCHO, RT. 4 h 10%
(MeOM’’
FP co
D
C
O 64%
H
L
Feltl
THF
Olson, A.S.; Seitz, W.J.; Hossain. M.M. Terruhedron Lell., Z991, 32, 5299. n CI Nd
0
-@
t-Bu
-
C12C=CHCI, 55°C. 48 h
\==
t-BU
CHO
80%
A.&; Scherbakova, I.V.; Taek, R.D.; Steel, P.J.Can. J. Chem., 2992, 70, 2040.
Also via P-Hydroxy aldehydes: Section 324 (Alcohols - Aldehyde).
SECTION 342: AMIDE
- AMIDE
(yg H
*
0
Beckwith, A.L.J.; Dyall, L.K. A m . J. Chem., 2990, 43, 451.
> 0
Ph
N.Me
1. LiNTMSz , THF 2. aq. Ht
95%
0
phf c
0
NHMe NHMe
ph,,.t
0 (70:30 threo:erythro)
70%
w o v . I.V.; Smushkevich, Y.I.J . Chem. SOC., Chem. Cotnmun., 1990, 1686. Ph-
H-N
N-H
NH2
DMF ,aq. dioxane , 10 min
Bannworlh. W.; Knorr, R. Terrahedron Lerr., 1991. 32, 1157.
376
Compendium of Organic Synthetic Methods, Vol8
1.2.5 eq. LDA ,THF
MeHN Ph
NHMe
Ph
Ph
Ph
NHMe Ph
(4
1)
Enda.;Shudo, K. Tetrahedron Leu., 1991, 32,4517.
50%
Section 312 (Carboxylic Acid - Carboxylic Acid) Section 350 (Amines - Amines)
Also via Dicarboxylic Acids: Diamines
SECTION 343: AMIDE
Section 343
- AMINE
b.:Me (ipr)2Nl 1. LDA
Me0
0
(~PI-)~N
63%
O E
2.
Ph
\=N Alcaide. B,; Plumet, J.; Rodrfguez-Lopez,J.; Shche-Cantelejo, Y.M. Tetrahedron Lett., 1990, 31, 2493. 1 . 0 ~ 0 ,4NaIO4 ,NMMO 2. Et3Si1, TFA D-
78%
Holladav. M.W.; Nadzan, A.M. J. Org. Chem., 1991, 56, 3900.
(CO),Crl
NMePh
H
CO ,ether, hv
Sijderberg, B.C.; l k g & ~ L LJ. Org. Chem., 1991, 56, 2209.
Etgbv, J.H,; Qabar, M. J. Am. Chem. SOC.,1991, 113, 8975.
H
Amide - Ester
Section 344
-
c)
N C02Me
Ph4;
, CHC13
NH-NHC02Me
+
RT ,70 min
377
80% Vidal, J.; Drouin, J.; Collet...!.Chem. SOC., Chem. Commun., 1991, 435.
0
Me
CQ
R
H2N /L N H z , A1203
'b' CO,E~
microwaves (125 W) * 15 min
Pilard, J-F.; Klein, B.; Texier-Boullet. F.; Hamelin.
Me 90%
0
J, SynLett, 1992, 219.
REVIEWS : "The Chemistry of Pyrazolidinones" Org. Prep. Proceed. Int.. 1991, 23, 275. Claramunt, R.M.;
SECTION 344: AMIDE
- ESTER
PMB = p-methoxybenzyl Clark. R.D.; Souchet, M. Tetrahedron Lett., 1990, 31, 193.
Na
MeOzC-kCqMe NHAc
Ph
~
OAC
91:g ( 4 C02Me:
2
P
Ph
[ ( Z - C ~ H ~ ) P ~ CMe02C ~]~ COzMe THF , S-BINAP NHAc 120 h ,25"C 92% +
h
Me02C
IIII
COzMe )
A Ph
C02Me NHAc
(95%ee , S) Yamamchi, M.; Shima, T.; Yamaeishi. T,; Hida, M. Tetrahedron Letf., 1990, 31, 5049.
04 N 0 -C 0 z t - B ~ Boc Schoenfelder, A.;
==/-OH
THF , R T , 24 h
Maon.
CO2t-BU
,KCN *
t-Bu02C+NHBoc
Synth. Commun., 1990, 20, 2585.
77%
Section 344
Compendium of Organic Synthetic Methods, Vo18
378
OH
ACO ,r-Bu
1.2 LDA .TMF
(96
4)
85%
Hatanaka.;Park. 0-S.; Ueeda, I. Tetrahedron Lett., Z990, 31, 7631. Me Me
1. phv N-Ts , Tic14
C H F l z , RT
MeoAco2Et Me0
Me
Me
N
Ts
2. EtOH
Me
TS'
Ph
(98
mCPBA , DCC ,DMF 2S°C, 1 h
k02Bn
Ph 2)
UK.; Shimada, S.; Hasegawa, M. Chem. Lett., 1990, 905.
f i C02H O N
Me
+ O G C02Et
04)-Co&t
81%
o + j Q
*
0%ester with free lactam Shiozaki. M,Synthesis, 1990, 691.
c1 42%
'02Bn0
K CH(C02Me)2 , 110°C Mn(OAch, AcOH 10 min
47%
Tetrahedron Lett., 1991, 32, 1011.
del Rosario-Chow, M.; Ungwitayatorn, J.; 1. NaOAc , OsC13 30% MeC03H
H
NHB&
RT
Go*'
0
H
78%
2.5%Na2SO3 Murahashi.; Saito, T.; Naota, T.; Kumobayashi, H.; Akutagawa, S. Tetrahedron Leu., Z991, 32, 2145.
OH
1. Pb(OAc)4 ,EtOAc ,M S 4A 2. DABCO
SEt 86%
Apitz, G.; U l i c h . W. Tetrahedron Lett., 1991, 32, 3163.
Amide - Ester
Section 344
379
1. RuC13-3 H20, NaOAc , AcOH MeCHO, EiOAc , 40°C, 3 h + 2.10% aq. Na2S03
0&(Me H
72%
Murahashi.;Sdto, T.; Naota, T.; Kumobayashi, H.; Akutagawa, S. Tetrahedron Left., 1991, 32, 5991.
Boc-Trp-COOH
+
H2N-Trp-OMe
new peptide coupling reagent
DMF ,iPr2NEt ,RT , I .5 h , - F
K0
96%
Ph- P. Ph F
Chen, S.; Xu,J. Tetrahedron Lett., 1991, 32, 6711
F 0 NHTs
Boc-Trp-Trp-OMe
c
w
PdClz , CuC12, NaOAc CO , MeOH-AcOH ,3OoC
Co2Me
N*Ts
0
I (
87 h
89%
0
(1:7 cis:trans)
Tamaru. Y,; Tanigawa, H.; Itoh, S.; Kimura, M.; Tanaka, S.; Fugami, K.; Sekiyama, T.; Yoshida, Z. Tetrahedron Lett., 1992, 33, 631.
so-
O I y
[aceLophenoneLDA]
C02Et
THF
c
OH 0 phA.A/yC02Et
78%
BOC NHBoc Ezauerra J,; de Mendoza, J.; Pedregal, C.; Ramirez, C. Tetrahedron Lett., 1992,33,5589.
LN.
BOc RhdOoctvl)4, pent& _... L,----,
d o A c o 2 E t
N2 (66% dr , 1R)
Davies.;Huby, N.J.S. Tetrahedron Lett., 1992, 33, 6935. 1. “NaPhSeBHj” ,heat 2. H+ ,CH2N2
OSiPh2r-Bu Pedersen, M.L.;
-
OSiPh,t-Bu SePh 85%
Tetrahedron Lett., 1992, 33, 7315.
Compendium of Organic Synthetic Methods, Vol8
380
0 Ts(Me)N>
9
-
1. TfzO , -($-Bu
-
Section 344
C H g 1 2 , -lOOd-BU
2.RT.
75%
N(Me)Ts
3. H f l , C C 4 , RT 4. mCPBA , NaHC03 CHzClz ,0°C
(93%ee)
Genicot, C.; Ghosez. L Tetrahedron Lett., 1992, 33,1351.
Abe, M.; Sudo, A.; Hasegawa, A. Chem. Lett., 1992, 1445.
Shimada, S.; -K;.
Siozaki. M. Synthesis, 1990, 691.
0
)-CHO
COzMe
M e 0 P 4NHCbz
Me0
CO2Me
DBU ,CH2C12 , -2OOC + RT
NHCbz
quant.
(3:97 E:Z)
Schmidt.;Griesser, H.; Leitenberger,V.; Lieberknecht. A.; Mangold, R.; Meyer, R.; Riedl, B. Synthesis, 1992, 487.
C02Me CI+NHCHO Me
2 'W
0
Roos, E.C.; JIiemstra. L;-0. SynLett, 1992, 451. Related Methods:
SiMe3, TMSOTf , 4 h
*
@CO*Me \ NHCHO 84%
W.N.; Kaptein, B.; Kamphuis, J.; Schoemaker, H.E.
Section 315 (Carboxylic Acid - h i d e ) . Section 316 (Carboxylic Acid - Amine). Section 351 (Amine - Ester)
SECTION 345: AMIDE
NHBoc Nemoio, H.; Jimenez, H.N.;
- ETHER, EPOXIDE, THIOETHER 4% RhH(PPh3)4, MeOH sealed tube, 100°C +
9NHBoc OMe
M%
J. Chem. SOC., Chem. Commun., 1990, 1304.
h i d e - Ether
Section 345
a t
C02Me
38 1
-
1. NBS , hv , 1 5 min
Cc4 ,CH$32.
2. EtOH 2,641tidine
9
0
EtOA CO2Me 41%
!%m. C.J; Pitt, M.J. Tetrahedron Lett., 2990, 31, 3471. n-CloH21
4
HBF4, H2NCOzEt 4 5 T . 10 h
+
Ane OH l
NHC02Et Et0,CHN
PhSe
SePh 25%
61%
0
Francisco, C.G.; Hernhndez, R.; Le6n, E.I.;Salazar. J. A%;SuArez, E. J. Chem. Soc., Perkin Trans. 1, 1990, 2417.
3
O
+
phs>Me PhSH ,hv
N
O
b
r
v
L
N
S
P
h
L 12% (2:l cis:trans)
54% (trans)
Naito.; Honda, Y.; Miyata, 0.;Nonomiya, I. Heterocycles, 1991, 32, 2319. 2% VO(dpnh, 02,DCE iBuCHO , RT, 12 h
MM e u y . P h
0
*
MeG~' 87%
Me
Me
0
Me
VO(dpm)r = bis-(dipivaloy1methanato)oxovanadium (IV)
Inoki, S.; Takai, T.; Yamada, T.; Mukaiyama. T. Chem. Left., 2991, 893. TolSo2NH2, PhSeCl , DCE 85%
cat. ZnClz/elher, 24 h
. .
Toshtmltsu.; Kusumoto, T.; Oida, T.; Tanimoto, S. Bull. Chem. Soc. Jpn., 1992, 64, 2148. Me2NCH0, N3C02Et
AOSiMe,
heat
* &OWNMe
CHO
Mitani, M.; Watanabe, K.; Tachizawa, 0.; Koyama, K. Chem. Lett., 2992, 813.
38%
382
Compendium of Organic Synthetic Methods, Vol8
SePh
I .
NHCO2Et
j30,Et
(87 Cooper, MA.;Ward. A.D. Tetrahedron Lett., 1992, 33, 5999.
SECTION 346: AMIDE
Section 346
13)
95%
- HALIDE, SULFONATE -78°C
0
NIS = N-iodosuccinimide cossV.;Thellend, A. Tetrahedron Lett., 1990, 31, 1427.
Cl2, H20,90"C 39%
H
H Ranc. E O r g . Prep. Proceed. Int., 1990, 22, 104. 5% Pd(0Ac)z. RT 2 eq. benzoquinone 2 eq. LiCl , 8 h
c1
acetone -H20
(>98%cis) Backvall. J -B; Andersson, P.G. .I. Am. Chem. SOC., 1990, 112, 3683.
Me
c1H
~
0
BuNH2
0 ~
Cundida t cylindrucea lipase
Me+
c1
NHBu
62% (95% ee) Gotor..,Brieva, R.;GonzBlez. C.; Rebolledo, F. Tetrahedron, 1991, 47,9207. Brieva, R.; Rebolledo, F.; -.I. Chem. SOC., Chem. Commun., 1990, 1386 [with subtilisinl.
Amide - Ketone
Section 347
0
383
1. LiN(SiMq)Z
Me OMe
OMe
(1
Araki, K.; Wichtowski, J.A.; N!ekhJL
Tetrahedron Lett., 1991, 32, 5461.
O
1. LDA
0 i N X B U
HMe o
O
t
0"
N
O L B
3.5) 68%
u
HMe F
Ph
88%
Ph
(97% de)
0 2
Davis. F.AA;Han, W. TetrahedronLett., 1992, 33, 1153. 12, s-collidine , RT
0 Ph-
\
NEt,
CH2Cht18 h
I Kitagawa, 0.;Hanano, T.; Hirata, T.; Inoue, T.;
_id
12, THF
*
84%
Tetrahedron Len., 1992, 33, 1299.
'
d)+&$
0
MeS \ N
Bn I
in
Bn
I
56%
4% D h h a t a . H,; Wang, E-C.; Ikuro, K.; Yamazaki, T.; Momose. T, Heterocycles, 1992, 34,435.
SECTION 347: AMIDE
6
Si(iPr1,
N
- KETONE
1. ROCOCl 2. MeMgCl , -78°C
PhMeITHF 3. H30+
R = 8-phenylmenthol
*
hcl bcl
M~'''\ I?
+
C02R
Me
major
92% (91% de)
N
COzR minor
Comins. D.L.; Guehring, R.R.; Joseph, S.P.; OConnor, S. J. Org. Chem., 2990. 55, 2574.
3 84
Compendium of Organic Synthetic Methods, Vol8
Section 347
0
1.
0
MeOH , CH2CI2 2. pyridinium p-toluenesulfonate CH2C12, reflux, 1 h 5821.
0
; Henke, S.L.; Luce, P.; Nakanishi, E.; Schulte. G. .I. Org. Chetn.. 1990, 55,
GN
ETn
1. Bn-N=C=O , NaN ,THE
2'H20
O
*
U
N 75%
Ognyanov, V.I.; Hesse. M.Helv. Chitti. Acra, 1990. 73, 272. 1. Ac.BF4-bIeCN
d d L
%
2.aq.NaOH Gridnev, I.D.; Balenkova, E.S. Zhur. Org. Khitn., 1990, 26, 46 (Engl., p. 37). MeO-
OSiMe,
N * Cbz 1-Bu
TMSOTf
*
&
304%
Cbz I
t-BU
85%
Earle, M.J.; Fairhurst, R.A.; Heanev. H,; Papageorgiou, G. SynLeft, 1990, 621. 1.20% HC1
NHiPr 2. MsCl , Bu4N HSO4 C02Me H20/CHC13
Buchholz, R.;
Ph
iPr
Helv. Chini. Acta. 1991, 74, 1213. PhI(02CCF3)2 , MeOH RT, 10min
* -0
NHAc 76%
Kits.; Tohma, H.; Kikuchi, K.; Inagaki, M.;Yakura, T. J. Org. Chetn., 1991, 56, 435.
385
Amide - Ketone
Section 347
Linde, R.G. 11; Deroncic, L.O.;
J. Org. Chem., 1991, 56, 2534. Rh2(0Ac)4 , CHC13 25°C ,45 min
0
79% 0
Padwa.;Chinn, R.L.; Hornbuckle, S.F.; Zhang, Z.J. J. Org. Chem., 1991, 56, 3271. 0
0
0
1. TIC4 , CH2C12
iPrZNEt, 0°C , 1 h b
Bn
2.
&
0
OAN&
Bn
-25"C, 0.75 h
Me
88%
(>99: 1)
Evans. D.A,; Bilodeau, M.T.; Somers, T.C.; Clardy, J.; Cherry, D.; Kato, Y. J. Org. Chem., 1991, 56, 5750. hv ( h = 313 nm) , MeCN
k
N. B0 nBZ
( l o 2 M) , 7 5 min
z* B::&
70%
0
Le Blanc, S.; Pete, J-P.;Piva. 0, Tetrahedron Letf.,1992, 33, 1993.
230°C, 5 h
cossV.;Bouzide, A. Tetrahedron Left., 1992, 33, 2505.
Me
(85
15)
95%
Compendium of Organic Synthetic Methods, Vol8
386
3
Section 349
1. NEt3 , Me3SiCI NaI , MeCN
2. MeNHSOZCI , NEL MeCN Vega, J.A.; Molina, A.; Alajm'n, R.; Vaquero, J.J.; Garcfa Navlo, J.; A l v a r e z - B u i u Tetrahedron Lett., 1992, 33, 3677. BQO, DMF ,55"C
Ph
3h
Ph
ShiDton. M .R. SynLetr, 1992. 491.
SECTION 348: AMIDE
- NITRILE
*
Ph
NC
8OoC, 17 h
fL
b
c
P
?
NC
h
+
"Me
fi.,.Ph
NC
Ac (5
N, "Me Ac 1)
Teng, M.; Fowler. F.W, J. Org. Chem., 1990. 55, 5646.
NC
CO,Et
1. LiNHBn , THF , -70°C 2. EtOH *
NC h N H B n 0
Bhawal, B.M.; Khanapure, S.P.; Biehl. E.R. Synth. Commun., 1990, 20, 3235.
SECTION 349: AMIDE
- ALKENE
Phfi'N% 93% Georg.;He, P.; Kant, J.; Mudd, J. Tetrahedron Lett., 1990, 31, 451.
3%
0
A HCO~AC 'pp:
ONH:O
Baldwin.;Aldous, D.J.; O'Neil, LA. Tetrahedron Lett., 1990, 31, 2051.
75%
80%
Amide - Alkene
Section 349
0
1.LDA.THF
4N'n-Bu
A J
387
0
0
+ fiI+pBu
2.% xylene k H,4hn - B u 135°C (99.5
0.5)
:
92%
Tsunoda.;Sasaki, 0.; It8, S Tetrahedron Lett, 1990, 31, 727. Me H-CiC+Me OH
2
C%.BuNHz
*
PBu3, 110°C
56%
BU"'fo
0 Fournier, J.; Bruneau, C.; Dixneuf, P.H. Tetrahedron Lett., 2990, 31, 1721.
qN,o 3.85%HQ04
n-C6Hi3 N-H
H
PhMe , 60°C
Me Barluenpa.; Tom& M.; Subez-Sobrino, A.; Rubio, E. Tetrahedron Lett., 1990, 31, 2189.
*
\
see Tetrahedron Lett., 1988, 29,4855
PhCHO , PPh3 iPrOH ,reflux * 48 h
Me
N-BW
Ph9NH Me 71%
EZ) Dellaria, J.F. Jr.; Sallin, K.J.Tetrahedron Lett., 1990, 31, 2661. (2:l
1. LiN(TMSh ; TMSCl THF , 0°C
-pJ
=CHO
2. c , L 3. xylene, reflux, 20 h
Uvehara.; Suzuki, I.;
57%
Tetrahedron Lett., 1990, 31, 3753.
pTol-N=C=O
dioxane
N- To1
0
76%
Ljebeskind.;Johnson, S.A.; McCallum, J.S. Tetrahedron Lett., 1990, 31, 4397.
Compendium of Organic Synthetic Methods, Vo18
388
B
NHBoc n o A O
Section 349
0
1. t-BuMeZSiOTf 2.6-lutidine
H'NKo
h 2. TBAF ,THF ,RT
10%Pd(PPh3)4, 1 h
78%
BnO
(9:l syn:anti) Spears, G.W.; Nakanishi, K.; Qhfune. Y,Tetrahedron Lert., 1990, 31, 5339.
8h
KnaDD.; Gibson, F.S.; Choe, Y.H. Tetrahedron Len., 1990, 31, 5397.
84%
Ru BuMgBr
Bu C02t-BU
C02t-Bu
+ BF3oOEt2 + CuBr
+ 0) 100)
(100
(0
63% 77%
Shono. T,; Terauchi, J.; Ohki, Y.; Matsumura, Y. Tetrahedron Letf., 1990, 31, 6385.
BocHN-CHO
1. (CHz=CH)2ZnCI 2. A c ~ O 3. HzC(COZEt)z,NaHPd(PPh3)4 , THF
CO,Et
B~~HN-
--
CO,Et
87% ThomDson. W.J,; Tucker, T.J.;Schwering, J.E.; Barnes, J.L. TefruhedronLeff.,1990, 31, 6819. 1. THF, KH , -78°C
/y
H k
p
Ph 0
3
-Br
2. MeCN , 105°C 12 h
0S,2
CCl,
Ph
70% (4 diastereomers) 51:31:12:7 syn ax.:anti ax.:anti:eq.:syneq. Guv. 4; Crailiot, Y . Terrahedron Left., 1990, 31. 7315.
Amide - Alkene
Section 349
389
1. RuC12(PPh3)3
PhH , t-Bu00H 2. Na bisulfite
C02Me
C02Me Naota, T.; Nakato, T.;
89% Tetrahedron Lett., 1990, 31, 1475.
'
PhI , NEt3 , 3% Pd(0Ac)Z
C02Me
C02Me
Nilsson, K,; Hallbere. k J. Org. Chem., 1990. 55, 2464.
fi N
SiMq
S ~ C I ~
*
CH2C12, -78°C. 30 min
CO2Et (50
CO2Et 1) 90%
&
W k o w s k i . A.P,; Park, P. J. Org. Chem., 1990, 55, 4668. ,DMF KOAc ,8O0C. 4 d Bu~CI
Larock.;Yum, E.K. SynLett, 1990, 529. PhN,
1. PPh3 , PhMe , RT 2. adipoyl chloride, PhMe
reflux, 3 h
-
-
0
45%
cN:Ph
Aubert, T.; Farnier, M.;sjuilard. R, Synthesis, 1990, 149.
77%
c1
1. Ac*BF4-MeCN
2. MeCN
3.aq.NaOH
&WAC
60430%
Gridnev, I.D.; Balenkova, E.S. Zhur. Org. Khim., 1990, 26, 50 (En& p. 40).
390
Compendium of Organic Synthetic Methods, Vo18
(3
x
0
-
Section 349
1. LDA ,THF ,-78°C
2.
Br
77%
Diels- Alder reportedpreviously Chockalingam, K.; Harirchian, B.; BaUJlL Synth. Commun., 1990, 20, 189.
Braisted, A.C.; Schultz. P.G, J. Am. Chem. SOC.,1990, 112. 7430. 1 . 1 2 , THF 2. NaH , DMPU ,THF
NHTs DMPU = N,Ndimethylpropylene urea Shaw, R.; Anderson, M.;
I
+s
+
"41 TS
83%
10%
SynLett, 1990, 584.
Yamapuchi.; Hamasaki, T.; Utimoto, K.; Kozima, S.; Takaya, H. Chem. Lea., 1990, 2161.
Bz. N
-78°C -+ 55°C
Kim. D.; Kim, H.S.; Yoo, J.Y.Tetrahedron Letr., 1991, 32, 1577.
62%
Section 349
Amide - Alkene
Ph-CkC-H
39 1
hNEt2
5% PdCIz(PPh,),, 5% PPh3 10%Me1 ,NHEtz , 120°C
-
CO (5 a m ) , 6 h
Ph
81%
0 Torii.;Okumoto, H.; Sadakane, M.; Xu, L.H. Chem. Lett., 1991, 1673.
Giesler, A.; Steckhan. E.; Wiest, 0.;Knoch, F. J. Org. Chem., 1991, 56, 1405.
Co&
- 1 3 g , so2
*
a surfactant diene \ H 2 0 * ' o h
X
o,,,,,,
e n - T * H 1 302s_ \ 0 - n ~ ~ 1 3 02s \ Ph
x o
-+
Ph
x o
(80
X = NHCOz(CH&NMq+ Bf
20)
98%
laeper.,Shinozaki, H.; Goodson, P.A. J. Org. Chem., 1991, 56, 2482.
(i+
1
!J 0
2eq. MezAICl CHzClz ,-30°C
-
Snider. B.B,;Zhang, Q. J. Org. Chem., 1991, 56, 4908.
(-$ 0 , Me
OMe
*
BX
0'Li+
THF ,reflux, 12 h
e I
Me (5.5
Coates, B.; Montgomery, D.;
a Me (64%) p Me (14%
Me 1)
Tetrahedron Lett., 1991, 32, 4199.
64%
Section 349
Compendium of Organic Synthetic Methods, Vol8
392
phi
0 xylene ,reflux
N
0
(>95:5
YPh
76%
H
E:Z)
Janecki, T.; &&l&JL ' Tetrahedron Lett., 1991, 32,6231.
5 q.A c ~ O
*
H o
- Hy
60%
H
0 OMe tralI. ; w c . W.N Tetrahedron Lett., 1992, 32,6633. Roos, E.C.; Bemaw. P.; IL.
Q
HZN
OMe
m4(c0)12,DBU t-BuMezSi-H ,CO
t - B u M e 2 s i p
PhH , 100°C
C&-H
H
oQo
64%
Sakakibara, J.; Nagashima H. Tetrahedron Lett., 1992, 32, 743 1.
-
RuHz(PPh3)4, DME HzO , 120°C , 2 4 h
94%
H Sasao, S.; Saito, E.; Naota, T. J. Org. Chem., 2992, 57, 2521.
;-
CSCH2 0
K 0
NHTs
PdClZ(PhCN)z, THF N E t 3 , RT
+C1
-
f
-
oyN- Ts 0
P 53%
Kimura, M.; Fugami, K.; Tanaka, S.; ~&MJLX,J. Org. Chem., 1992, 57. 6377. Tetrahedron Lett., Kirnura, M.; Kure, S.; Yoshida, Z.; Tanaka, S.; Fugami, K.; 1990, 31, 4887 [with CuCI, NEt31. Terrahedron k t t . , 2991, 32, 6359 [with Kimura, M.; Fugami, K.; Tanaka, S.; AgNCO] .
Amide - Alkene
Section 349
0
393
0
PhCHO , PPE , 2 4 h 35°C
Ph
I
63% Me PPE - see J. Org. Chem., 1969, 34, 2665 Marson.;Grabowska, U.; Walsgrove, T. J. Org. Chem., 1992, 57, 5045.
Me
A. ph 0 N' bMe Et
5% PdC12(PhCN)2 THF,20°C, 16h
1
c
N-Ph
0
79%
Metz.;Mues, C.; Schoop, A. Tetrahedron, 1992, 48, 1071.
0
OTf , DMF , K2C03
-f
Co2H MCbz
=
&yC02H
10% Pd(OAc)z, Bu~NCI
20% P(o-Tol)3 Criso.;Glink, P.T. Tetrahedron, 1992, 48, 3541.
0 p
EtO- , EtO
77%
NHCbz
0
n-C6H13CHO, ether n-C&,3 a N . ~ ~80% e NaH ,0°C + RT /
he
7 P . . 0 M e94% 0 Me
l h
(955 E Z )
Netz, D.F.; Seidel. J.I. Tetrahedron Lett., 1992. 33, 1957.
&(cH2)8NHBoc
2. 1. 3. TFA NMI hv ()i=340 nm)
CHzC'2
(
2 0
0
52%
Ouinkert. G.; Nestler, H.P.; Schumacher, B.; del Grosso, M.; Diirner, G.; Bats, J.W. Tetrahedron Lett., 1992, 33, 1977. = / C 0 Z M e DME , ,02
'H
5% PdC12(MeCN)2 5% CuCl ,60°C Hosokawa. T,; Takano, M.; Kuroki, Y . ;Murahashi. S-I. Tetrahedron Lett., 1992, 33. 6643.
Section 349
Compendium of Organic Synthetic Methods, Vo18
394
l.PhCH0, PhH ,80°C (Dean-Stark) 2.4 eq. NaBH4, MeOH Ph 3. AcCI, NEt3 A c - N J 60% 4. PhCHO, THF ,TBAF RT (35:65 E Z ) Palomo. C. ; Aizpurua, J.M.; Legido, M.; Picard, J.P.; Dunogues, J.; Constantieux, T. Tetrahedron Lett., 1992, 33, 3903.
Fn
H 2 N y SiMe3 SiMe3
*'
Bu /
OSiPh2t-Bu cat. PdC12(PhCN)2
0
>N-H
OSiPh2t-Bu
*
PhH
72%
C13C
(88% ee)
cc13
Mehmandoust, M.; Petit, Y.;Larchev&que,M. Tetrahedron Lett., 1992,33,4313.
0
f
MedN
1.LHMDS.THF -78°C
Ph
2. 120-C , 6h
+
Me4
Me (92
8)
-8
80%
Tsunoda. T.; Sakai, M.; Sasaki, 0.; Sako, Y.;Hondo, Y.; It& S. Tetrahedron Lett., 1992, 33, 1651.
0 X
OSiMe3
1.
hosiM,e;" H
2. 02, ether
\ /
X = C02Me
Wv.J.H,;
87%
Ateeq, H.S.; Krueger, A.C. Tetrahedron Lett., 1992, 33, 5873.
Q ,CHzC12, -8OOC
%&% Ph
Ph
-
lMgI2 ,24 h
m e v . E.J,; Ishihara, K. Tetrahedron Lett., 1992, 33, 6807.
N
0
O 82%
(9554.7 enantioselectivity) (97:3 endo:exo)
Amide - Alkene
Section 349
H-CI C ~ N H T
395
1. BuLi ,THF 2. 5% Pd(0Ac)z. THF S 10% PPhj 3 . 3 eq. PhI ,60°C
& Ph N
c
is
57%
Luo. F-T,; Wang, R-T. Tetrahedron Dtt., 1992, 33, 6835.
I
0
3. PhN=C=O 4. aq. NaOH
Kataoka, Y.; Oguchi, Y.; Yoshizumi, K.; Miwatashi, S . ; Takai. K,; Ytimoto. K,Bull. Chem. SOC. Jpn., 1992, 65, 1543. Takai. K.; Kataoka, Y.; Yoshizumi, K.; Oguchi, Y.; Utimoto, K, Chem. Lett., 1991, 1479.
0
10% Pd(0Ac)z , THF 2 q.CuC1~,02,6OoC 24 h
Anderson, P.G.; Backvall. J-E.J. Am. Chem. SOC.,1992, 114, 8696.
9
BrbN .Bu3As PhCHO
0
ph
> N S
25% Pd(PPh3)d 0
30%
Shen. Y.; Zhou, Y. Synth. Commun., 1992, 22, 657. Zheng, J.; Wang, Z.; D e n . Y. Synth. Commun., 1992, 22, 1611 [with Zn, B u ~ P70%]. ,
0
0
f i c ~ oPh3PCH2C3H7 Br
O
N
BuLi , THF
Smith. M.B,; Kwon, T.W. Synth. Commun., 1992, 22, 2865. REVIEWS :
"N-Dienyl h i d e s and Lactams: Preparation and Diels-Alder Reactivity" Smith. M.B, Org. Prep. Proceed. Int., 1990, 22, 315. Also via Alkenyl Acids: Section 322 (Carboxylic Acid -Alkene)
Section 350
Compendium of Organic Synthetic Methods, Vol8
396
SECTION 350: AMINE
- AMINE
Rossi.;Celentano, G.; Stradi, R.; Strada, A, Tetrahedron Lett., 1990, 31, 903. N H ~ PhCHO ,TFA PhH ,reflux
Dean Slark trap
H H Narayanan, K.; Cook. J.M. Telrahedron Lett., 1990,31, 3389.
75%
Uenishi, J.; Tanaka, T.; Wakahavashi. S;,@gJ.,Tetrahedron LRtt., 1990, 31, 4625. 1. LiI
4.Mefl-0
Me
Chamchaang, W.;
I
BnHN
I 3 n h u U . .I. Org. Chem., 1990, 55, 2531. MeNHCH2COzEt
Ph NMe2
Me2N&
c
NaOEt ,EtOH ,20h
reflux Krolikowski, D.A.; Yu, R.H.; Riesinger, S.W.; 1990, 55, 4135.
;-
Ph
.
phh N I Me '
coZEt
87%
J. Org. Chem.,
1. NH3, Pd-C , EtOH , 12 h
NY .
40%
Ph J. Indian Chem. Soc., 1990, 67, 470.
+
NH2
Ph , ) , , NH,
80%
Arnine - Amine
Section 351
1.2 eq. SmI2 ,65"C 2. H2O
Ph7\ N- Ph
397
Ph+ph
b
1. SmI2 ,THF ,reflux 2. MeOH , silica gel
93%
NHPh
Imamoto.:Nishimura, S. Chem. Lett., 1990, 1141. Bn
NHPh
*
69%
F.nholm. E.L; Forbes, D.C.; Holub, D.P. Synfh. Cornrnun., 1990, 20, 981.
Ph
H O T OHPh Oi, R.;
Ph
xso2
>:
Ph_4N-H
N H ~
Ph
DMF, reflux 15 h
Ph
Tetrahedron Lett., 1991, 32, 999.
Me P h , rj
1$H
Ph N 72%
Me
BuLi , ether ____c
Ph
N ~ N - N M ~ , Me
Me
H
60%
eN;;
(>99% de)
Alexakis. A,; Lensen, N.; Mangeney, P. Tetrahedron Lett., 1991, 32, 1171.
a
Me 1. N2O4, ether (28%) 2. H 2 , Pd(OH)2IC
*
Me 97% Zhang, W.; Jacobsen. E.N. Tetrahedron Lett., 1991, 32, 1711.
Me
1. P B u ~PhH , 2. BH3, THF
91%
Takeuchi, H.; Matsushita, Y.;
J. Org. Chem., 1991, 56, 1535.
398
Section 35 I
Compendium of Organic Synthetic Methods, Vo18
fl
@
1. S n , 12 N HCI 2. NaOH ,CH2C12
*
NO2
&Ma; Nakayama, I.; Wilson, R.B.
NH2
82%
Jr. J. Org. Chem., 1992, 57, 778.
1. PhNCO ,PhMe ,reflux
30 rnin
oNa
b N = p p h : PhMe ,reflux, 20 h d N H P h 45% Noeuchi.;Onimura, K.; Isomura, Y.;Kajigaeshi, S. J. Her. Chem., 1991, 28, 885.
oNH2
1. oxalyl chloride ,THF reflux 2.NaBH4,TFA * PhHN25OC Nutaitis. C.F. Synth. Commun., 1992, 22, 1081.
NHPh
13%
REVIEWS:
"The Chemistry of 1,3-Dioximes" Kotali. A.; P w oreiou. V.P, Org. Prep. Proceed. h i . , 1991, 23, 595.
SECTION 351: AMINE
- ESTER
B q S n H , AIBN PhMe .9O0C ,8h
C02Me 92%
(35:65cis:trans)
Esch, P.M.; Hiemstra. &;Speckamp. W.N, Tetrahedron Lett., 1990, 31, 159.
M e O G C02Me b-. C0,Me Skrinjar, M.;
-
BuCu Bs
Bu'"
n rlJC o 2 M e + C02Me (96
Tetrahedron Lett., 1990, 31, 1115.
N
Bu
C0,Me
C0,Me 4)
84%
Amine - Ester
Section 35 1
E~O~C,,,,CO~E~
MeqC02Et
LiMe2Cu ,ether -78°C
N
399
c
+s
8
NHTs 68%
EtO2C
Tanner. D,; Birgersson, C.; Dhaliwal, H.K. Tefrahedron Lett., 1990, 31, 1903.
*
Boc-NHNH2
.
80%
MeCN reflux
ONs
NHNHB~~
ONs = 2-nosyloxy - 2-(((4-nitrobenzene)sulfonyl)oxy) Hoffman. R.V.; Kim, H - 0 . Tetrahedron Left., 1990, 31, 2953. 1. LDA ,THF , -78°C 2. DIOP (-) , -50°C. 4h
SOWY, 0
80% (99% de)
Ph C I - e P d
Ph
Genet, J.P.; Kopola, N.; Juge, S.; Ruiz-Montes, J.; Antunes, O.A.C.; Tanier, S . Tetrahedron Lett., 1990, 31, 3133. 1. methyl acrylate
2. B u S n H
*
Q ' Co2Me
LN \
83%
C02Me 12%
Boivin, J.; Fouquet, E.; &ad. S.Z, Tetrahedron Lett., 1990, 31, 3545.
Ph,C= N-(
C02Me
OAc
NaCH(C02Me)z MeCN ,25'C, 2 h
cat. Pd(PPh3)4 =- P I I , C : N - ~ [ O ' ~ ~
Me02C
CO2Me
ODonnell, M.J,; Yang, X.; Li, M. Tetrahedron Left., 1990, 31, 5135.
MOM0
N
1.3 L D A , THF -78°C
C02t-Bu . .
2. BnBr
MoMQ
-P
CO,t-Bu
Ph
Wdllams.;Benbow, J.W. Tetrahedron Lett., 1990, 31, 5881.
66%
79%
Section 35 1
Compendium of Organic Synthetic Methods, Vo18
400
P(OEt)3 ,PhMe
RT 73%
Luheshi, A-B.N.; Salem, S.M.; U l l e v , R.K. Tetrahedron Lett., 1990, 31, 6561.
A
1. LiBr, D B U , THF
NYCO,Me Me
AN&C02Me 2*
M 6 C02Me
-COzMe
61%
Kanemasa.;Uchida, 0.; Wada, E. J. Org. Chem., 1990, 55,4411,
*
ye
LDA*Bn2NCH2C02Et, THF
C02Me
c
-78°C
f i NBnz
Me02C
threo selective Yamaeuchi.; Torisu, K.;Minami, T. Chem. Lett., 1990, 377.
-
OSiMe3
Phv N-Ph
MeAOMe
,-78°C
5% TrSbCb, CH2CIz 15 min
NHPh
+
*Ph
NHPh phhc02Me
Me
Me 8)
(92
other Lewis acids used, with varying selectivity Mukaiyama, T.; Akamatsu, H.; Han, J.S. Chem. Lett., 1990, 889. Kato, K.; Mukaiyama, T. Chem. Lett., 1990, 1917.
NHC02SiMe,t-Bu
Me02C
c1
2 eq. AgF ,MeCN RT , 2 4 h
M:02C
56%
co2Et
95%
0
0
9 9
H.NK*
(3 Sakaitani, M.; Qhfune. Y. J. Am. Chem. SOC., 1990, 112, 1150.
+
H.
K N O
Me02C
2)
63%
NBn2 hv , co (60 psi), MeOH C02Me c M e 4 87% (CO),Crd NBn2 Me Ileeedus.;Schwindt, M.A.; DeLombaen, S.; Imwinkelried, R. J. Am. Chem. SOC.,1990, 112,2264.
Section 35 1
40I
Amine - Ester
flCo2'
O
Ru-C , AcOOH
t
H
G O A c O H
82%
Murahashi. S; Naota, T.; Kuwahara, T.; Saito, T.; Kumohayashi, H.; Akutagawa, S. J. Am. Chem. SOC., 1990, 112, 7820. Ti(OiPr)4 , TMSN3 CH2C12, RT , 2 h
Me3Si0 tn
OAC 70%
Sutowardoyo, K.I.; Sinou. D, Bull. SOC. Chim. Fr., 1991, 128, 387.
N.OH
10%Co (salen derivative) BuONO , PhSiH3, THF
--
-0Bn 0
+OBn
RT.47h
Kate.; Mukaiyama, T. Bull. Chem. SOC.Jpn., 1991, 64, 2948. Kato, K.; Mukaiyama, T. Chem. Letr., 1990, 1917.
1. BnO2CCH2NHS02Ts1 r-BuOK 2. POC13 , Py
0
Me
La&). T.D.;
=
3. t-BuOK
89%
0
Me
Q,o,,n H
Hoehner, M.C. J. Her. Chem., 1991, 28, 1671.
Mertin, A.; Thiemann, T.; Hanss, I.; &J&j&gA
9
Bn' N,CHO Bn Pe cam. A.E.;
SynLerf, 1991, 87.
1. ( i P r O ) C l 2 T i . 3 OEt 24 h , 0°C
-
2. AcOH , PhMe
35%
*
B n2N Bn (>20: 1
good yield 4R,5S)
Kawaguchi. A.T.; Vofante, R.P.; Shinkai, I. Telrahedron Len., 1991, 32, 1867.
Compendium of Organ;:: :ynthetic Methods, Vo18
402
Section 35 1
EIO~CI(CHO
Nz
PhCN
2% Rh2(0Ac)4 45% 7OoC, 6 h Connell, R.D.; Tebbe. M.; Helaulst. . P ; hermark, B. Tetrahedron Lett., 1991, 32, 17. n-C6H1
THF ,-10°C
- N.SiMe,
3-
t-Buo2Cwn-C6HI
*
+t-Buozcw Y n-C6H1 3
Y
pPLi c1 Of-Bu
H
H
(100
0)
52%
Cainelli, G.; Panunzio, M.; Giacomini, D. Tetrahedron Lett., 1991, 32, 121.
0
Bz
1. 1.1 eq. LDA
"02CEt
NHBz
\
2. THF'ooC7 CH2N2, THFhh
54%
Bz O N o M e
+
M ,e Me
39%
Endo.;Hizatate, S.; Shudo, K. Tetrahedron Lett., 1991, 32, 2803. (CO2F-t
TSFA , PhH ,5"C 7h
NO2 -d.
C@Et
w
HO'
N 4
Ph
70%
TSFA = triflic acid J-M.; Jacquesy, J-C.; Violeau, B. Tetrahedron Lett., 1991, 32, 3075.
,&
1. BrySMe2, NEt3
CH2C12 , -20°C
C02Me + Ph 2. mCPBA , CH2C12 -20°C Ph NHPh 85% 3. MeC07Me, LDA -78°C Palomo. C,; Cossio, F.P.; Rubiales, G.; ApAricio, D. Tetrahedron Lett.. 1991, 32, 3115.
R
wN
C02Me
C02Me
CuCl , DME 2,2-bipyridine
*
(&:2Me b02Me
47% (30:70)
+
5
N C02Me C02Me 12%
Udding, J.H.; J&umaJL ; van Zanden, M.N.A.; SoeckamD. W.NTetrahedron Lett., 1991, 32, 3123.
Amine - Ester
Section 35 1
403
LDA ,EtONO
Moorhoff, C.M.;
CH=NOH CO2Et 46%
THF - pet ether
0
J. Org. Chem., 1991, 56, 703.
Meo2c9CEC-H 1. NaH, THF 2.
Me02C
Ph
3. reflux Tavlor.,Macor, J.E.; French, L.G. J. Org. Chem., 1991, 56, 1807
C02Et
Me2N-
PhCHO ,LDA BEt3, -20°C
-
OH
Ph+CO@l GMe2
+
41%
OH ph&C02Et
NMq
CHo
1. BnNH, 2. NCS
rn
r..~
3. 1.3 I-BuOK ,R r ether, 5h
/
De Kimpe. N.; Yao, Z-P.; Boeykens, M.; Nagy, M. Tetrahedron Len.,1990, 31, 2771. N.Bn - ~ r
J'
Ph
THF
,cat.TiCi4 7
A h
*
P
h
c
83%
Tanaka,H.; Inoue, K.; Pokorski, U.; Taniguichi, M.; Toni. S. Tetrahedron Left., 1990, 31, 3023. ,OBn AlBN,80°C
2. AcOH ,MeOH
&
(Bn0)HN
1. BusSnH, PhH
*
82%
C02Me
Enholm. E.J.; Burroff, J.A.; Jarmillo, L.M. Telrahedron Left., 2990, 31, 3727.
Ding, Z.;
Synfh. Conimun.. 1990, 20, 227.
416
Compendium of Organic Synthetic Methods, Vol8
phq
Section 356
BuLi , THF
NHMe
Ph'($b
-78°C -+ -loo(?
Ph
-/'
85%
LiAIH4 86% Tetrahedron Lett., 1990, 31, 5353.
Tokuda.;Fujita, H.;
\:hP
he
Ph
0
-?
1. C N - H
CN
b
0
2. NaN(TMS)2 3. i K H O
81%
~ L ~ & Merino, & L JI.;.Palacios, ; F. Tetrahedron Left., 1990, 31, 6713.
Tsuda.;Kiyoi, T.; -.I.
Org. Chern., 1990, 55, 3388.
K2C03, H 2 0 , CS2 TEBA , CkIzC12
wph
W " - O H Albanese, D.; Landini, D.;
=C-(
Bn SMe
Synthesis, 1990, 333.
iPrCH=NBn , AIC13 , PhMe
RT
52%
81%
(3: 1 cktrans)
Hayashi, Y.; Shibata, T.; Narasaka, K. Chem. Lett., 1990, 1693.
',""?
PhNHZ*HCI 140°C
60%
Abdrakhmanov, I.B.; Gataullin, R.R.; Mustafin, A.G.; Tolstikov, G.A.; Baikova I.P.; Fatykhov, A.A.; Panasenko, A.A. Zhur. Org. Khim., 1990, 26, 1527 (Engl., p. 1319).
Amine - Alkene
Section 356
Et2N
NHEt2, MeCN
Ets---lfCF3
RT,2h
0
417
74%
0
Hoio. M; Masuda, R.; Okada, E. Chem. Lett., 1990, 2095. 1. TfOH , -78°C
NHPh
2. PhNHEt .21"C
*
3.80°C
72%
4. Me-CS-Me 5.H'
Grossman, R.B.; Davis, W.M.; -..I.
(>95% ee) Am. Chem. SOC., 1991, 113, 2321.
5 eq. n-C3HT-CS-n-C3H7
H
NH2 5% Pd(OAc)*, 5% PPh3 DMF , 2 4 h
Larock.;Yum,E.K. J. Am. Chetn. SOC., 1991, 113, 6689.
\ S , F ~ CSF Ph-
THF.RT.15h .
80%
NHPh
I
Ph-CH=N-Ph
n-C3H7
I
94%
Me
(74:29 erythro:threo)
Kira.;Hino, T.;
Ph'Na
'
Chetn. Lett.. 1991, 277.
Cu , PhMe , reflux 4h
+
Ph
9
)=c
0
Ph
70%
(82:18 E:Z)
Sekiguchi. M.; Ogawa.; Kambe, N.; SQU&L.&
Chetn. Len., 1991, 315.
I . BuLi , iPrlNH, t-BuOK 12 h , -5OOC
Me,Si-
N(SiMe3)2
2, PhCHO, -50°C + RT
Me3Si c-
Me3Si*
Nk Ph
Degl'Innocenti, A,; Mordini. A,; Pinzani, D.; Reginato, G.; Ricci, A. SynLett, 1991, 712.
418
Compendium of Organic Synthetic Methods, Vol8
m
1. LDA ,THF 2. MeCHO , -78°C + RT
Schuster, E.; Hesse, C.;
Me Ph
F3C
32%
SynLett, 1991, 916.
*Br
.ether
>Np'h
Bocoum, A,; Boga, C.; Savoia.;
k
*
3. DCC , cat. CuCl , ether 3h
N
PhA'NX
Section 356
'
H (4357diastereomers)
Tetrahedron Lett., 1991, 32. 1367.
Ne fh dPh ,P m e , ~
2 ~ 0 3
Pd2(dba)yCHC13 6S"C, 26 h
F3C
Unevama.~.; Watanabe, H. Tetrahedron Left.,1991, 32, 1459.
W'uts. P.Q.hL; Jung, Y-W. J. Org. Chern., 1991, 56, 365. Bu$nH, AIBN , ACN PhH ,reflux, 3 h
-Q+
slow addition of tin hydride
A C N = azobis(cyc1ohexane)carbonitrile
65%
Zlegler.; Jeroncic, L.O. J. Org. Chem., 1991, 56, 3479.
TNY L
quant.
0.3 eq.HCI , dioxane 1 0 l ° C , 20 h
Cook, G.R.; Stille. J.R, J. Org. Chetti., 1991, 56. 5578.
N+
95%
Amine - Alkene
Section 356
419
-o$g 0
PhI(02CCF3)2 CF3CH20H RT ,30 min
N
H o
H
o
51%
Kita, Y,; Tohma, H.; Inagaki, M.; Hatanaka, K.; Kikuchi, K.; Yakura, T. Tetruhedron Lett.,
1991, 32, 2035.
n
H-C’C%Me
0 N H LJ
Hg(OAc)z,NEt3 THF , Rr
Kr:;f-
Katritzkv. A.R.; Long, Q-H.; h e , P. Tetrahedron Lett., 1991, 32, 3597.
0
OSiMe2t-Bu CDC13
.t
BU
.SiMel
= N,
56%
AiC13
Tanino, K.; Takahashi, M.; Murayama, K.; Kuwaiima. I. J. Org. Chern. 1991, 57, 7009.
, 40%aq.HCHO
MeCN ,TFA
0 0
Gregoire, P.J.; Meilor.;Merriman, G.D. Tetrahedron Lett., 1991, 32, 7099.
420
CompenJ:um of Organic Synthetic Methods, VOI8
N(SiMe,), H-CE C--/ Corriu. R.J.P,; Bolin, G.; More-
1. Bu$nH, AIBN 2. PhBr ,PhMe 2% Pd(PPhj)q, 72 h
Ph
W NHz 65%
Terrahedron Left.. 1991, 32, 4121.
1. PhNHMe
OH
m
Section 356
2’ Y B r BiClyAI , aq. THF*
-L
NMePh
85%
Kalrilzkv.;Shoban, N.; Harris, P.A. Tefrahedron Lett.. 1991, 32, 4247.
Neumann.;Rogic, M.M.; Dunn, T.J. Terrahedron Lett., 1991, 32, 5865. n
10 eq. HCOOH THF
0
49%
0 Rutjes, F.P.J.T.; Paz, M.M.; Hiernstra. K; Sneckamn. W.N, Tetrahedron Lett., 1991, 32, 6629.
1. xylene/PhMe , -78°C Tic14 2. LiAIH4
71%
Cook, G.R.; Bark, N.S.; .I. Org. Chem., 1992, 57,461. J. Org. Chem., 1992, 57,7188. Barta, N.S.; Cook, G.R.; Landis, M.S.;
\ QNHTs Harris, G.D. Jr.; Herr, R.J.;
5% Pd(OAc)z, DMF P(o-T01)3 ,NazC03
N B u ~ C I75”C, , 22 h
meTS
Me
J. Org. Chem., 1992, 57,2528.
67%
Amine - Alkene
Section 356
1. LDA , THF , -78°C 2. (EtO)2POCI
42 1
85%
fln-CdH9
+
n-C4H9
4. hexanal Hiehet. R.J.; Jones, T.H. J. Org. Cheni., 1992. 57, 4038. Sn[N(iPr)z] , ether
FJN3 ph+CHO
w
Ph-
N(iPr)2 70%
Burnell-Curly, C.; Roskamn. E.J, J. Org. Chem., 1992, 57, 5063.
Meq
Bu3SnH. AIBN THF ,reflux
N - Phth
D
LN
16%
1)
(1
Tefrahedron, 1992, 48, 1317.
Dickinson, J.M.;
TFA , CHzClz
* G0 > S i Me Me3
96%
Me
OoC
Gelas-Mialhe, Y.;Gramain, J-C.; Louvet, A.; Remuson, R. Tefruhedron Left.. 1992. 33, 73.
*
Pd(PPh3)4, K2CO3 , 2 h
~
H
B H
Arcadi, A.; Cacchi. S,; Marinelli, F. Tetrahedron Leff.,1992, 33, 3915.
Me
(c"'c'
NHBn
2 eq. MeCHO ,MeCN 5 eq. B u ~ N I120°C , *
2 eq. MeS03H , 18 h
& ef. N Me Bn
Overman. L.E,; Sarkar, A.K. Tetrahedron Leff.,1992, 33,4103.
71%
82%
u
Section 356
Compendium of Organic Synthetic Methods, Vol 8
422
P
Me0
NHt-Bu
N- t-Bu
heat
* Y
w; De buck, K.; Booten, K . Tetrahedron Lett., 1992, 33, 393. 1 . Pd(PPh3h H ~ N CO (40 psi) 55°C
(-JOT'
HO
2. soc12
t
m,
Mevers. A.L; Rohichaud, A.J.; McKennon, M.J. Tetrahedron Lett., 1992, 33, 1181. 1. TfOSiMe$-Bu ?h , 2OoCc Q Ph
OSiMe,
Ph
+
P
OSiMe-,
better selectivity-lower yield with AlCb
Ph
OSiMe3
(54
28)
86%
e
92%
Nogue, D.; Paugam, R.; Wartski, L. Tetrahedron Lett., 1992, 33, 1265. 1.9-BBN
Me3Si
N @ CHO
Me)=C=
W
3. NaOOH , 1 h
(98:2
M Z:E)
Tetrahedron Lett., 1992, 33, 5025.
Sattsangi, P.D.;
SiMe3 c
Et
hv , DCN , MeCN:H20 10 h
70%
Pandev. G,; Rani, K.S.; Lakshmaiah, G . Tetrahedron Lett.. 1992, 33, 5107. 1. CF3S03H , 0°C
CH2CI2
b
2. NaOH
&won. N!.H.; Schkeryantz, J.M. Tetrahedron Lett., 1992, 33, 5291.
71%
Amine - Alkene
Section 356
90%
1. acetyl bromide ,ZnCI2 2. ZflHFIDMSO 3. CuCN , 2 LiCl ,O°C
CHO
4. THF , LiCl , -78°C +Br
Chou, T-S.;
Me
B u a B r , -2.1 V
95% C02Et
J. Org. Chem.. 1990, 55, 4791. 1. deposit on Celite powder
la2-lo4 mbar
57%
Enereaction Choi, S.S-M.; JCirbv. G.W.; Mahajan, M.P.J. Chem. SOC., Chem. Commun., 1990, 138. PhI(OAc)z , HBF, , 6 h
%CN
& OAc 0
+
aq. AcOH
0
83%
Tiecco. M; Testaferri, L.; Tincoli. M,; Bartoli, D. Tetrahedron, 1990, 46, 7139. 1. p-NBSP
-
OSiMe3 2. NaOAc , DMF ,60°C Me/-\OMe
MeYCozMe 33% OAc
p-NBSP = p-((nitrobenzene)sulfonyl)peroxide
Hoffman. R.V.; Stoll, D. Synth. Commun., 1991, 21, 211.
L
A
SPh
C02Me
"base", DMF -78°C
* / F h
*-
C02Me
(>90% de)
Rodriguez, C.M.; Martfn, V.S. Tetrahedron Let?., 1991, 32, 2165.
88%
426
Compendium of Organic Synthetic Methods, Vo18
0.
10%PdC12, cuc12 1 a m . C O , RT, 1 d
OH
Section 357
111
-
propylene oxide, MeOH MeC(OEt)3 , CH2C12
C02Me
55%
Tamaru.;Hojo, M.; Yoshida, Z. J. Org. Chem., 1991, 56, 1099. LiI , DMF
"'C02Et
40 min
61%
3 : 0 2 E t
Kasalkin.; Kulak, A.N.; Tolstikov, G.A.; Shitikova, O.V. Tetrahedron Lett., 1991,32, 4591.
1. SrnI2, THF , O°C 2. A c P DMAP w
aoAc phx 68%
C02Me
Br
Inanaea.;Yokoyama, Y.; Handa, Y.; Yamaguchi, M. Tetrahedron Lett., 1991, 32, 6371. S d 2 - T H F . HMPA MeOH ,RT
C 0 2 M e 70% C02Me
Ph
(1.91 dr)
Inanaga.;Handa, Y.; Tabuchi, T.; Otsubo, K.; Yamaguchi, M.; Hanamoto, T. Tetrahedron Lett., 1991, 32, 6557.
C02n-C,SH2 5 porcine pancreatic lipae
A
H COz1-Bu
28 h
~
r-BuO,CLrC)c 0
o +
37% (49 l e e )
I C02t-B~
Sbi. M.P.; Gaboury, J.A. Tetrahedron Lett., 1992, 33, 5681. e' , PI cathode/Cu anode NaI , 0. I M Et4NC104
77%
DMF
(36:64 tramcis)
Tokuda. M.; Hayashi, A,; Syrinome. H,Bull. Chern. SOC.Jpn., 1991, 64, 2590.
Ester - Ether
Section 358
427
IOeq. -CO2Et , AIBN 0.1 Bu$nCl, t-BuOH
EtO
2 eq. NaBH3CnI reflux
I
0
Stork.;Franklin, P.J.Aust. J. Chem., 1991, 44, 275.
65%
Bi(OAc)3 , I2
6 " O A c -I- 6 , , A c OAc OAc (70
30)
71%
Trainor, R.W.; Deacon, G.B.; Jackson, W.R.; Giunta, N. Aust. J. Chettz., 1992, 45, 1265. Also via Dicarboxylic Acids: Section 312 (Carboxylic Acids - Carhoxylic Acids). Diols Section 323 (Alcohol - Alcohol) Hydroxy-esters Section 327 (Alcohol - Ester).
SECTION 358: ESTER
- ETHER, EPOXIDE, THIOETWER
Yadav. J.S,; Rao, E.S.; Rao, V.S.;Choudm. B.M, Tetrahedron Len., 1990, 31, 2491. 2 iodosobenzene , TMOF conc. H2S04, overnight w
Ph
Ph
TMOF = trimethylorthoformate Sineh. O.V. TetrahedronLett., 1990, 31, 3055.
PhSe+Co2Et CO,Et
=/
n-C6H13
hv (sunlamp), PhH* reflux
XMe
C02Me 82%
Eto2ue
EtO2C
Bvers. J.H.; Lane, G.H. Tetrahedron Lett., 1990, 31, 5697.
95%
n-C6H 13
Compendium of Organic Synthetic Methods, Vol8
428
Ph
2
1. p l y L-leucine ,H202 NaOH , CC14
Baures, P.W.; Eggleston, D.S.; El.&&J&
B
0 0
ph 2. mCPBA , CH2C12
JJ, Tetrahedron Lett., 1990, 31, 6501.
,
o
~
. .OTf
Section 358
Ph
m
OPh
56% (>99%ee) ; Gombatz, K.; Lantos.;Mendelson, W.; Remich.
O Me'''
Me'
0
C0,Me
80%
Witty, D.R.; Feet. G W L , Choi, S.; Vogt, K.; Wilson, F.X.; Wang, Y.; Storer, R.; Myers, P.L.; Wallis, C.J. Tetrahedron Lett., 1990, 31, 6927. 1. HOOCCH2C02Me ,CH2C12 DCC , DMAP ,30°C 2. TsN3, MeCN , NEt3
SPh
3. Rhz(OAc)3 , PhH , reflux
M e h O H
*
MePo 40%
PhS Et0,C
Kido, F.; Kazi, A.B.; Yosh ikoshi. A. Chem. Lett., 1990, 613.
(1%OH
n-C7Hl~Br,MeCN , 100°C KCNO, Bu4NBr
Tomesch, J.C.; Houlihan, W.J. Synthesis, 1990, 477.
; .M-
61%
Jarvis, B.B.; Wells, K.M.; Kaufmann, T. Synthesis, 1990, 1079. 1. = r O H CH2C 12
EtO-
\
COEt
.ms
2. Cr(OAc), , aq. THF
RT
(1:3.9 cis Me:trans Me) Lubbers, T.; Schafer, H.J. SynLelr, 1990, 44.
Section 358
Ester - Ether
MeO-0
K0
429
Rhz(MEPY)d, CH2C12
CHN,
reflux
*
oJ
62%
OMe
(91% ee, S) Dovle. M.P.; Van Oeveren, A.; Westrum, L.J.; Protopopova, M.N.; Clayton, T.W. Jr. .I Am. . Chem. SOC., 1991, 113, 8982.
t-Bu
,t-Bu
BnEt3NCI. CHC13 K2CO3, H 2 0 . 3 h
* j y/ N 0
oxone, pH 1.5
O2N
83%
O2N
Bulachkova, A.I.; Koldobskii, G.I.; Drozdetskii, A.G.; Tereshchenko, G.F. Zhur. Org. Khitn., 1991, 27, 215 (Engl., p. 189). BF30OEt2, -78°C + 0°C
OMe Ph
*
OMe
Me0
0
Ph
40SiMe3 C02Et
CO2Et
86%
Sugimura. H,; Shigekawa, Y.; Uematsu, M. SynLett. 1991, 153. PPTS , EtOAc
H t-Bu cyclohexane t-BuH:To HOJ''Me ' ~ ~ 0 Dean-Starlctrapc H H 80°C
x
Co2H
it-Bu
Me
Chapel, N.; Greiner. A,; Ortholand, J-Y.Terrahedron Lett., 1991, 32, 1441. Greiner. A,; Ortholand, J-Y. Tetrahedron Len., 1990, 31, 2135.
Et
59%
BunSnH ,AIBN , PhH reflux , 6 h
=cT 0
(Jh
Me 3)
(97
CO2Et
CO2Et
(35:65 cis:&ans)
77%
80% E Loikema, L.D.M.; Hiemstra. H, ; Ghouch, A.A.A.; Speckamn. W.N. Tetrahedron Lett., 1991, 32, 1491.
EtO' 0 P-( I'
EtO ;-
.
Section 358
Compendium of Organic Synthetic Methods, Vol 8
430
C02H SMe
12.. 2 eq. T BuLi C H, THF O , -78°C
-
HO
A
68%
3. H30'
.
Midura, W.H. SynLetr, 1991, 245.
SynLett, 1991, 771.
Kornaisu, M.; Suehiro, I.; Horiguchi, Y.;
# 0
b m
1. (TBDMS-OTf/NaMn(CO)5]
2. =/ COzMe 3. hv 4. CSA Rybczynski, P.J. .I. Org. Chetn., 1991, 56, 3207.
Me*Me
BnSH , BuLi THF ,0°C
C02Me
*
0
76%
Me
Me
MeHMe + BnS
BnS
(98
C02Me 2)
98%
Miyata, 0.;Shinada, T.; Ninorniya, I.; Nruto.; Date, T.; Okamura, K.; Inagaki, S.J. Or& Chem., 1991, 56, 6556.
OBn OBn
HO,,+OH
4 eq. Cundidu cylindruceu
OBn OBn A~O+OH
hexanes ,0005 M
OBn
d
OAc
,2S0C,48h
OBn (98% de)
Bureess.K.; Henderson, I. Tetrahedron Lett., 1991, 32, 5701.
CSPh 1. Zn ,AcOH ,60°C 2. NaCl , DMSO/H 150°C
@ h:
COZEt
56%
Kido.;Kawada, Y.; Kato. M.; Yoshikoshi, A. Tetrahedron Lett,, 1991, 32, 6159.
58%
Ester - Ether
Section 358
43 1
OMeOMe
M e O l C02Me
&C02Me
SnCb , BTMSA CHfllz, 20°C, 2 b
-+
Me0
0
BTMSA = MeA N ( S i M q h
Earle, M.J.; Fairhurst, R.A.; &mey&
COzMe 74%
3.9)
(6.1
Tetrahedron Lett., 1991, 32, 6171. 1 . (PhTe)2,NaBH4 EtOH
'COzMe
MsO-
9 OMe
CI
PyS"&O2Me
*
-
()
54%
Barton.;Dalko, P.I.; Gero, S.D. Tetrahedron Lett., 1991, 32, 4713. 0
-4.-
CO,Et
t
Mn(OAch
Mellor. J.M.; Mohammed, S. Tetrahedron Lett., 1991. 32, 7107, 7111.
53%
1. LiNTMSz , THF
-78°C ~ RT Me 2. TMSCI , - 7 8 -+ 3. TMS-OTP
-
Wilson, L.J.;
SPh (3.7:l trans:cis)
J. Org. Chem., 1992, 57, 1948.
0 -/S-Ph
,WAA
-
TFA , -20°C 4RT ,24h
Brichard, M-W.; Janousek, 2.; Mereny, R.; Brichard, M-H.; Musick, H.; Janousek, Z.;
0 F 3 C 2 ' "
Tetrahedron Lett., 1992, 33, 251 1.
w,H.G. Synth. Cornmun., 1990, 20, 2379. C0,Me
1. iPrCu(MgBr2) ,-1 5°C 3h
2 : x : h
H
65%
2. CH2N2 (94% dr)
Heckmann, B.; Mioskowski. C,; Yu, J.; F a l c k . , Tetrahedron Left., 1992, 33, 5201.
432
Compendium of Organic Synthetic Methods, Vo18
N2=CHC02Et, C H s 1 2 cat. RhzfOAck
- G
0 , BocHN BocHN Hlavacek, J.; Kral, V. Coll. Czech. Chern. Cornrnun., 1992, 57, 525.
-
o^..
5% Pd(OAc)z
ACO,, *
2 eq. p-benzoquinone
/
Section 359
c0,Et
&
83%
87%
H
Bgckvall.;Anderson, P.G. J. Am. Chern. SOC.,1992, 114, 6374. TI(OAc)3 , PhH ,reflux
OH
(OAc 0
83%
Mihailovik, M.Lj.; Vukikvik, R.; r
HO
+
G C - H CO , DBU, 100°Cc Rh2(CO)n
0
79%
H
O OHC
L SiMe2t-Bu
6%
Matsuda. 1,; Ogiso, A.; Sato, S. .I. Am. Chem. Soc., 1990, 112, 6120. IrHs(P[iPr13 - PBu3
C: C- C02Me
PhMe ,80"C, 30 h
Ma, D.; Lu,& Tetrahedron, 1990, 46, 3189.
c-
-C02Me 87%
450
Compendium of Organic Synthetic Methods, Vo18
Section 362
( B z O ) ~reflux , (3huanp. C-P.SynLet1, 1990, 527.
Batty, D.; Crich. D, Synthesis, 1990, 273. e- (Pt electrodes) , 2 4 h
'-
/-yo0
Kbpy)(trpy)R~OI+~ pH 8 buffer
42%
trpy = 2,2',6,2"-terpyridine
Camps, J.L.; De Giovani, W.F.;
Synthesis, 1990, 597.
4C02Me
PhSSPh , THF , reflux
dco2Me 81%
(98:2 EZ) Miyata, 0.;Shinada, T.; Ninomiya, I.; paito. T, Synrhesis, 1990. 1123.
0 EtO- PEtO
0
C02Et
0
,LiBr
NEt3 ,25"C
Rathke. M.W,; Bouhlel, E. Synth. Commun., 1990, 20, 869.
-
Br2C(C02Et)2, THF 2 eq. BuzTe, 50°C
PhCHO
~
Ph-
CO2Et
CO2Et
93%
Zhou, Z-L.; Shi. L-L,; Huang. Y-2,Synth. Commun., 1991, 21, 1027.
BCl,
NzCHCOzEt, ether -65OC
Brown.;Salunkhe, A.M. SynLett, 1992, 684.
c
CO2Et
65%
Ester - Alkene
Section 362
cviy
45 1
MeOH ,80°C.
-
CQMe Me02C
Gruseck, U.; Heus&mnn. M, Chem. Ber., 1990, 123, 1911, 1905. 1. MezCuLi , elher, -20°C
Ph- Cr C\
CO2Et
2.2N H2SO.q. 25°C
c
M$ Ph*cyco~~ H
I(tause. N . Chern. Ber., 1990, 123, 2173. 1. 19% HCI , 25"C, 1 d 2. NEt3 , 25°C , 2 d
OH
c1
-*o
C02Me
66% (>96% ee)
Tsuboi. S,; Sakamoto, J.; Sakai, T.; Utaka, M. SynLeir, 1991, 867. 1. Pd(OAc)z, TEBA , K2C03 2. Ag2CO3, PhMe ,80°C 48% Arcadi, A.; Bernocchi, E.; Cacchi.; Marinelli, F. Tetrahedron, 1991. 47, 1525.
H- Cr c
Me02C
d
PhI , t-BuOK , DMSO 5% Pd(dba)z , 14 h Ic C02Me 30°C
Ph 80%
Fournet, G.; Balme, G.; Gore, J. Tetrahedron, 1991, 47, 6293.
4
C02Me
C02Me
20% BuSSBu hv (>300 nm)
4 Me02C Me02C
77%
Singleton. D.A,; Huval, C.C.; Church, K.M.; Priestley, E.S. Tetrahedron Lerr., 1991, 32, 5765.
452
Compendium of Organic Synthetic Methods, Vol8
CqMe
H-C5 C-CO2I3
=/
.AIDN c
Bu3SnH , PhH (0.2 M) reflux, 2 h
Bu3Sn
Section 362
C02Et +
u
62% (3:l Z:E)
31%
Lee.;Hur, C.U. Tetrahedron Left., 1991, 32, 5101.
O0
+
do
C1
Me
Li
COZLi ;
l.2. PhSOgI , Py * 92% 3. MgBn , CH2Cl2 BJack.;McDermott, T.S.; Brown, G.A. Tefrakedron Lett., 1991, 32, 6501.
TfO
66%
Pd(OAc)2, 2 PPh3
CO,Et TIIF, 55°C. 6 h IIounis. I.N, Tetrahedron Leu.,1991, 32, 6675.
,Me+ICI -78°C
(97.5:Z.S)
WS.; Cheng, X-M.; Chnprich, K.A. Tetrahedron Leu., 1991, 32, 6839.
(93 89% endo (2% exo)
Gras.;Pellissier, 11. Tefruhedron Lem, 1991, 32, 7043.
Ilofer, J.; Doucet, H.; Brmieau, C.; Dixneuf, P.H. Te/rahedron Leu., 1991, 32, 7409.
Section 362
453
Ester - Alkene
oo
0
0
EtO. P EtO
a SEt
0 *
NaH , TIIF, 20°C 19 h Liu, H-J.; Rose, P.A.; Sasaki, D.J. Can. J. Chem., 1991, 69, 934.
SEt
87%
NEt3, CO , MeOH
NHBn
RT,3h
c*
H
C02Me
Shaw, R.; Lathburg, D.; Anderson, M.; Gallagher, T. J. Chem. SOC.,Perkin Trans. I, 1991, 659. HCOOH , 120"C, 15 h
Bu-CZ C- H
[Ru(p-cymene)(PPh3)Cl2] *
Neveux, M.; Bruneau, C.; Philippot, K.; Devanne, D.;
BUTocHo 78%
J. Chem. Soc., Perkin Trans. I, 1991, 1197. J. Chem. SOC.,Chem. Commun., 1990, 1199.
1. C12CLiCO2Li 2. PhSOzCI, Py
3. MgBr2, ether
c
71%
B k k . T.R; McDermott, T.S. J. Chem. Soc., Chem. Commun., 1991, 184. Black.;McDermott, T.S. Synth. Commun., 1990, 20, 2959.
Ph 0
\
Fe(C0)4(acetone), PhMe 145"C, sealed tube, 60 h CO (55 psi)
87%
Pearson. A.L; Dubbert, R.A. J. Chem. Soc., Chem. Commun., 1991, 202.
cozMe, Ph- Cr C-Ph
Ru(COD)(COT) , 20 h
Mitsudo.;Zhang, S-W.; Nagao, M.; 598.
Py ,80"C
Ph PhAC02Me 87% J. Chem. Sac., Chem. Commun., 1991,
Compendium of Organic Synthetic Methods, Vol8
454
Me
Section 362
M~
Pd-SnC12 ,80"C DMI-H20 , 7 2 h
(96 Masuvama; Nimura, Y.; Kurusu, Y. Tetrahedron Lett., 1991, 32, 225.
1. AgOTf, CH2Cl2, RT
'Y0
4)
38%
~r
2. DBU , -78°C 63% (84:6:6:4)
Tahir, S.H.; Olrnstead, M.M.; &ut&ML Tetrahedron Let., 1991, 32, 335. BICH~CO~E P ~B,u ~ 25% Pd(PPh3)4 , 2 4 h
PhCHO (86:14
6CO+t
Ph
1 10°C -)
1OO:O E:Z for various aryl aldehydes
Shen.;Zhou, Y.Tetrahedron Lett., 1991, 32, 513.
:,& ''
i M H O , THF
0OEt 2266-telramethyl piperidine * p r i 2 E t +
Me
fi
85%
qi2E 8)
(92 Patois, C.; Savignac, P. Tetrahedron Lett., 1991, 32, 1317. OAc
=/
,NEt3
Pd(OAc)2, PPh3LDMF, 60°C , 7 h
Ciattini, P.G.; Morera, E.;
93%
Alto* I
(3.3:l EZ) Tetrahedron k i t . , 1991, 32, 1579.
79%
Ester - Alkene
Section 362
455
'uco2Me 1. I-BuOK 2. Pd(0) ,dppe
Me02C
1 q. t-B~0K/O"C124h 40 /20°C/9 h 35 0.2 q.t-BuOK/78"C/3 h 0 76 +18-crown-6 fl8"C/18 h Monteiro, N.; Balme, G.; Gore, J. Tetrahedron Lett., 1991, 32, 1645.
Ph/=
c=
C0,Me 43 75 0
45
CH2(C02Et)2, THF vinyl bromide, 65°C CH(CO,Et),
Pd(dbaI2ldppe
Ph
CH(CO,Et),
9)
(9 1
69%
p8%
(35:65 E:Z) Chaptal, N.; Colovray-Goteland,V.;Grandjean. C.; Cazes, B.; Gore, J. Tetrahedron Lett., 1991, 32, 1795.
M e 0M e2 0 C e
62 5% AIMe3, elher
Me02C
Harvey. D.F,; Brown, M.F. Tetrahedron Lett., 1991, 32, 2871.
Ph
OAc
13 k b a , CH2C12 7d
Prapansiri, V.;l&mkm&R
C0,Me
OTHP
(60:40 diastereomers)
*Ph
Tetrahedron Lett., 1991, 32, 3147.
Mkc
,NEt3,KBr 5% Pd(OAc)2,10% PPh3 aq. DMF ,70"C, 2 h n-C6HI 3
=/
Me n-C6H 13- C- CE CJ
76%
-
OC02Me 71% C02Me Mandai. T,; Ogawa, M.; Yamaoki, H.; Nakata, T.; Murayama, H.; Kawada, M.; Tsuii. J. Tetrahedron Lett., 1991, 32, 3397.
456
Compendium of Organic Synthetic Methods, Vol8
Section 362
XSMe Bu3SnH, AIBN PhMe ,80°C
lh
*
58%
4
C5-H a$ (9010) Iwasa, S.;Yamamoto. M,; Kohmoto, S.; Yamada, K. J. Org. Chem., 1991, 56, 2849.
(y*.* SePh
Ph3SnH. AIBN
C0,Et
CO2Et
H
92%
Clive.;Daigneault, S. J. Org. Chem., 1991, 56, 3801.
a
Davies. H.M.L,; Clark, T.J.; Smith,H.D. J. Org. Chem., 1992, 56, 3817.
H-CZC
PhI , CO (300 psi) , PhH Pd(0Ac)z , PPh3 ,NEt3 120OC. 24 h
OMe
Huang, Y.;A1Der.H..Org. Chem., 1991, 56, 4534.
5% PdC12(PhCN)2 AcOH ,RT
OMe
65%
Ph
clX t
0
81%
0
Ma, S.; J,u. X. J. Org. Chem., 1991, 56, 5120. Ma, S.; Lu. X. J. Chem. SOC., Chem. Commun., 1990, 733. BnO-OMe OMe
+
MewoMe 1. TMSOTf ,CHzClz
-78°C. 10 h
PhMqSi
Panek.;Yang, M. J.
C02Me 2. aq. NaHC03
Org. Chem., 1991, 56, 5755.
OMe
OMe
* B n o w C 0 2 M e Me
(30:l syn:anti)
8590
Ester - Alkene
Section 362
457
5)
(95
Takai.;Tezuka, M.;
76%
J. Org. Chem., 1991, S6, 5980.
x
,,,C02Me
C02Me (92% ee)
Devine, P.N.;Oh. T. J. Org. Chetn., 1992, 57, 396.
P h o O T f
+
c
cfC-H
CO2H
Pd(OAc)z( PP h3 )2 NEt3 , BqNC1 MeCN , 60°C 45 min
79%
*
Lqyh
0
0
74%
Arcadi, A.; Burini, A.; (3acchi.; Delmasuo. M.; Marinelli, F.; Pietroni, B.R. .I. Org. Chem., 1992, 57, 976.
75%
Pavies. H.M.L.; Hu, B . J. Org. Chetn.. 1992, 57, 3186. Pd(Pph&~.CO
OTf
*w
N B u 3 , LiCl ,65OC
0
83%
Crisn. G.T,; Meyer, A.G. J. Org. Chem.. 1992, 57, 6972. I.Mg*,THF,RT 2. acetone 3. c02 4. H30'
Mg* = activated Mg
Xiong, H.; Rieke. R.D.J.Org. Chem., 1992, 57, 7007,
68%
458
Compendhm of Organic Synthetic Methods, Vol 8
0
& csc-H
Section 362
Ph$nH, AIBN PhH ,reflux , 7 h 4 mM 63%
MQ-l
Baldwin.;Adlington, R.M.;Ramcharitar, S.H. Tetrahedron, 1992, 48, 3417. BrZnCHzCN , THF
P h Y C N OH
-13°C. 16 h
PhCHO
cat.
h Me
16%
(93% ee , S )
OH
Yang. S-K.; Kim, S-G.; Lee, J-S.TefrahedronAsymmetry, 1992, 3, 1139. =/
80"C
+
-CO,Me
4% N-methylpiperidine Ru(COD)(COT) 30 min also with conjugated amides
h
C0,Me
(90
10)
75%
Meo2cG.
Mitsudo.; Zhang, S-W.; Kondo, T.;
Ni(C0)4, f-BuOH
*
Me02C
Tetrahedron Leu., 1992, 33, 341.
Me02C Me02C
Llebarla.;Camps, F.: Morelb, J.M. Tetrahedron Lett., 1992, 33, 3683.
''Bonete, P.;
Ph- Cr C-H
1 . 2 eq. BuLi 2. iPrCHO
C02H
3. TFAA 4. DBU
Tetrahedron Lett., 1992, 33, 4065.
Pd(PPh3)4, PhH CO (15 atm) , 3 0 h 100°C
+ 0
(95
Itoh, K.;Miura. M,; Nomura, M. Tetrahedron Left., 1992, 33, 5369.
0 4)
Me 88%
Ester - Alkene
Section 362
PhCHO , CF12C12
0
alumina
459
w'"
-
0
93%
Varma.;V m , M. Tetrahedron Lett., 1992, 33, 5937. hv , EtOH ,O°C
Me
Me +
0
0
CqH
0
CO2H
(91
C W
9)
Charlton. J.L; Pham, V.C.; Pete. J-P, Tetrahedron Lett., 1992, 33, 6073. Piva, 0.;Pete. J-P. Terrahedron Lett., 1990, 31, 5157.
(2.3
1)
87%
Friesen. R.W.;Kolaczewska, A.E.; Khazanovich, N. Tetrahedron Lett., 1992, 33,6715.
Me- CE C- C02Bn
cat. Pd(OAc)z, RT
c
AcOH , LiOAc AcO 8.5 h Lu. X.; Zhu, G.; Ma, S. Terrahedron Lett., 1992, 33, 7205.
b
C02Bn 78%
1. LiN(SiMe3)z , DME 2. Cp2Zr(H)CI ,0°C -+ RT c
dcozM61%
Godfrey, A.G.; Ganem. B. Tetrahedron Lett., 1992, 33, 7461. ECHO , BzCl , EbNCl
SnMe3
Bu2SnC12
OB z
Yano, K.; Baba.;Matsuda, 11. Bulf. Chern. SOC.Jpn., 1992, 65, 66. Pd2(dba)3*CHC13
c-
OAc
AcOK , PPh3 , PhMe
77%
reflux OAc Trost.;Brieden, W.; Barringhaus, K.H. Angew. Chern. Int. Ed. Engl., 1992, 31, 1335.
Compendium of Organic Synthetic Methods, Vol8
460
O0 K0
Section 362
0
Bando, T.; Tanaka S.; Fugami, K.; Yoshida, Z.; T a m a r u . Y . u l 1 . Chetn. SOC.Jpn., 1992, 65, 97.
~ C - (H (M~CN)~[E-EIO~CCH=CHCO$~]~C~) H- N H-*cozE COZEt 4 O C - H I/CqE , PhMe , 0°C , 3 0 min Zhou, Z.; Costa.
86%
m, Chiusoli, G.P. .I. Chetn. Soc., Perkin Truns. 1, 1992, 1399. 1407. 1 . BulICuCN(Zn1
(80:20 cis:trans) Sidduri, A.R.; Knochel..I. Am. Chetn. Soc.. 1992, 114, 7579.
O
,TMSOTf,MeOTs
4 y o A
CH2C12, -4SOC
0
66%
0
(98:2 'para:meta') Mashimoto, Y.; Nagashima, T.; Ilasegawa. M.; Saipo. K. Chetn. Letf., 1992, 1353.
TBACN = tetrahutylammonium cerium (IV) nitrate Narasaka, K.; Okauchi, T.; Tanaka, K.; Murakami, M. Chent. Leff.,1992, 2099.
Bu
1.
BuCHO
C02Et
Sn , THF , aq. NH4Cl
2.
n+
0
Zhou, J.; Lu, G.; Wu. S . Synfh. Cornniun., 1992, 22, 481.
s 0
81%
Ether - Ether
Section 363
46 1
Related Methods: Section 60A (Protection of Aldehydes). Section 180A (Protectionof Ketones). Also via Acetylenic Esters: Section 306 (Alkyne - Ester). Alkenyl Acids: Section 322 (Carboxylic Acid - Alkene). P-Hydroxy-esters: Section 327 (Alcohol - Ester).
SECTION 363:
ETHER, EPOXIDE, THIOETHER EPOXIDE, THIOETHER
- ETHER,
See Section 60A (Protection of Aldehydes) and Section 180A (Protection of Ketones) for reactions involving formation of Acetals and Kecals.
acetone, MeCN , RT
0
"near quant." Bujons, J.; Camps, F.; I k k s u a A Tetrahedron Lett., 1990, 31, 5235. PhSeSePh , MeOH (NH&(O$O-OS03)
OH
G S e P h
reflux ,1.5 h
91%
Tiecco.;Testaferri, L.; Tinpoli.;Bartoli, D.; Balducci, R. .I. Org. Chem., 1990, 55, 429.
58% Mudryk, B.; Shook, C.A.; Cohen..l.Am. Chem. SOC., 1990, 112, 6389.
OMe
Ph
4OMe
5% PbBr;?, A1 , TFA
PhJe
THF ,1 h
OMe
Ph
83%
Dhimane, H.; Tanaka, H.; Torii. S. Bull. SOC.Chirn. Fr., 1990, 127, 283.
95% Sasaoka, S.; Uno, M.; Joh, T.; Imazaki, H.; 1991. 86.
'
.I. Chem. SOC.,Chenz. Commun.,
Compendium of Organic Synthetic Methods, Vol 8
462
e-50% , Pt anode, MeOH-THF LiC104
$ye
$,
+
Section 363
4:
Me0
Me0
(5.3
1)
73%
Moeller.; Manabadi, M.R.; New, D.G.; Chiang, M.Y.; Keith, S. .I Am. . Chem. soc., 1990, 112, 6123.
PhSeCi , CH2C12 RT,24h
OSiPh2t-Bu
c
p h ~ ~ ~ h 2 t - 1 3 u
PhSe"'
74%
(1:1.4 a$)
m g .
S.K; Hwang, T.S.; Kim, W.J.; Lim,J.K. Terrahedron Lett., 1991, 32, 4015.
CHO
Me3Si0v SPh
Me3SiSPh, -78°C 5% 'I'MSOTf .0.3 h CH2C12
93%
Kusche, A.; Hoffmann, R.; Munster, I.; Keiner, P.; Bruckner, R. Terrahedron Lett., 1991, 32, 467. 1. (MesSi)$iH, PhMe 2. AlBN , @O°C,1 h
*
-
3
oo-
S-Si(TMS)3 84%
Arva.~.; Lesage, M.; Wayner, D.D.M. Terrahedron Lett.,
-
1991, 32, 2853.
PhSSPh , PhSeSePh , hv
V
45"C, 30 h
S
m; Tanaka, H.; Yokoyama, H.; Obayashi, R.; Yokoyma, K.;
P SePh
h 74% .I. erg.
Chem., 1992, 57, 111.
OH
;-
PhSeSePh ,DCN , hv MeCN
*
P S e P h
Somasekhar, B.B.V. .I. Org. Chem., 1992, 57, 4019.
60%
Ether - Ether
Section 363
MeSeSeMe , SnC14 CH2C12, RT ,0.2 h
/--7
Me
'
MeSe
t
Me
Hermans, B.; Colard, N.;
463
SeMe
Me-Me
82%
Tetrahedron Lett., 1992, 33, 4629.
e- , Hg cathode , Pt anode N E t 3 , EkNCIO4, MeCN
O J o
85%
Br Bhuvaneswari, N.; Venkatachalam. C.S.; Balasuhramanian. K.K, Tetrahedron Lett., 1992, 33, 1499.
\y-J -.
9 I.+'
Bu3SnH. AIBN , PhH 80°C ,45 min -c
0B
0.
0B
Dalla, V.; I3k.P. Tetrahedron Lett., 1992, 33, 7857.
M e OCHC13 o T e f 1 3
* f ! O M e 98%
Comasseto, J.V,; Grazini, M.V.A. Synth. Commun., 1992, 22, 1061.
OMe n-C5H1 I-(
PhSeTMS , cat. TMSOTf CHzC12, -25°C. 15 min
*
OMe
OMe n-C5H,,
I 80°C
(3
quant.
1)
Detert, H.; Anthony-Mayer, C.;W A n g e w . Chem. Inf. Ed. Engl., 1992, 31, 791.
9
Ph’S&
i . NaOMe ,MeOH +
0 /Jcco,E3
2. CI3CC02H1A y O PhMe ,reflux 3. mCPBA ,CH~CIZ
c
QMe CO2Et
38%
Chan. W.H.; Lee. A.W.M.; Chan, E.T.T. $1. Chem. Soc., Perkin Trans 1, 1992, 945.
n-C,H,$CZ C
t-BuOK , t-BuOH 18-cro~n-6
t
MOM0
Marshall.; BuBay, W.J. J. Am. Chem. Soc.,
70% 1992, 114, 1450.
Ether - Alkene
Section 367
OHC
-
Ph 4ph
489
,Znlz, PhH
RT, 48 h
C
1
W
P
h
87% Ph CI Dvorak, D.; David, S.; Arnold, Z.; Ivana, C.; Petricek, V. Coll. Czech. Cheni. Commun.. 1992, 57. 2331.
(iPr),Si
Ri. iPr
1 . F-
'0
pri. .iPr
0
Bu o O M e
2. *siMe,C T ~ O H B(OTO)~ ~+ -5OC ,30min
Bu 1)
(23
85%
s. A.P.; Hegarty, S.C. .I. Am. Chem. SOC., 1992, 114, 2145.
HO
-3-
C=C-H
$
PhSH , Pd(0Ac)z THF ,67"C, 16 h
SPh
86%
Kuniyasu, H.; OPawa. A.; Sato, K-I.; Ryu, I.; Kambe, N.; Sonoda. N..I. Am. Chem. Soc.,
1992, 114, 5902.
Kuniyasu, H.; Ogawa. &; Sato, K-I.; Ryu, I.; Sonoda. N, Tetrahedron Lea., 1992, 33, 5525.
.
4 O ; N:
Bu-C€-SMe PhMe TiClz(OiPr)2 0°C
0
pet ether
U
*
92%
Bu
SMe (998% ee)
Narasaka.; Hayashi, Y.; Shimadzu, H.; Niihata, S. .I. Am. Chem. SOC., 1992, 114, 8869.
a1 OH
PhCECH , PdC12(PPh3)2 CUI, NEt3 , DMF 60°C, 16 h
m u . N . G ; Pal, M.; Mahanty, J.S.; Dasgupta, S.K. J. Chem. SOC., Chem. Commun., 1992, 41.
Ph
0
c1
B+*)
*
+
vo
EtdCI, DCE ,60°C Ph l h Yano, K.; Hatta, Y.; Baba.;Matsuda, H. Synthesis, 1992,693.
76%
490
Compendium of Organic Synthetic Methods, Vo18
Shimada. K.; Jin, N.; Fujimura, M.; Nagano, Y.; Kudoh, E.; 1843.
Section 367
Chem. Lett., 1992,
1.48%HBr , ZnBrz 5 eq. PhSH
OMe Kwon, T.W.;
2. Cu(0Tf)z ,NEt(iPr12 3.450"C
OMe
Synth. Cornmun., 1992, 22, 2213.
Ni, Z.; Padwa. A, SynLeft, 1992, 869.
Degl'Innocenti.;Ulivi, P.; Capperucci, A.; Mordini, A.; Reginato, G.; Ricci, A. SynLRtt, 1992, 499.
KOH. TBAB. ))>)>>I
-
Br
4:)
68%
Diez-Barra, E.; de la Hoz, A:, Diaz-Ortiz. A;, Prieto, P. SynLetr, 1992,893. Related Methods:
SECTION 368:
Section 180A (Protection of Ketones)
HALIDE, SULFONATE
- HALIDE, SULFONATE
I lalocyclopropanations are found in Section 74F (Alkyls from Alkenes).
IICOzNa, 4OoC
Hu.C-M,;Qing, P L . Tetrahedron Lett., 1990, 31, 1307.
87%
Section 368
Halide
- Halide
49 1
0.1
3 NIS , A1F3, DME 3 NH4HF2, 6O"C, lh
Ichihara.J.;Funabiki, K.; Hanafusa, T. Tetrahedron Lett., 1990, 31, 3167. BrCCl3, cat. SmI2 4nC6H 13
MeCN , 7 O 0 C , 10 h *
C13cvBr n-C6H 71%
13
Ma, S.; Lu. X,J. Chern. SOC., Perkin Trans. I, 1990, 2031.
; Fukushima, T.; Terakawa, Y.; Yoshida, M.; Sawada, H. J. Chern. Soc., Perkin Trans. I , 1991,627.
NIS , TBAH2F2
e
n-C10H21 CHzC12 , 0°C , y h
n-CloH21
87%
TBAHzF3 = tembutylammonium dihydrogen trifluoride
-
Kuroboshi, M.; Hivama. T, Tetrahedron Lett., 1991, 32, 1215. Kuroboshi, M.; Hiyama. T. SynLeft., 1991, 185.
n-CsH1 1
-1
BnEt3+ MnO4 , oxalyl chloride CH2C12, -40°C. 30 min
L C l ~2-CsH11
CH2C12 , 3 0 min
75%
Mark6, I.E.; Richardson, P.F. Tetrahedron Lett., 1991, 32, 1831. IPy2BF4.2 HBF4 CH2CI2, -60°C
I
-1
F
Barluenea.; Camps, P.J.; GonzAlez, J.M.; SuLez, J.L.; Asensio, G. .I. 56, 2234.
BrCC13, AcOH , AcOK Mn(0Ac)z ,RT * e- (0.06 F/mol)
c c 1 3 95%
78%
Org. Chern.. 1991,
Br
Nohair, K.; Lachaise, I.; Paugram, J-P.;Nedetec. J-Y, Tetrahedron Left., 1992, 33, 213.
492
Compendium of Organic Synthetic Methods, Vol8
SECTION 369: HALIDE, SULFONATE 0
- KETONE 0
MgBrpOEt,, elher
SiMe3 S02Ph
Me Hewkin, C.T.;
Section 369
Me)(CSiMea M e Br
2ooc*4
49%
Tetrahedron Lett.. 1990, 31, 1877.
P h y Sph
0
e- ,MeCN , Et$*3 HF ~t electrodes, RT
*
I . l O V , 1.6Frnol-'
Ph$SPh 84%
Brigaud, T.; Laurent E. Tetrahedron Lett.. 1990, 31, 2287.
4 0
Me Na
DMF , -65OC -+ RT overnight
0
Ymemoto. T.; Ishihara, S. Tetrahedron Lett., 1990, 31, 3579.
83%
Hoffman. R.V,;Wilson, A.L.; Kim, H-0. J. Org. Chem., 1990, 55, 1267. 2% RuC12(PPh3)3 PhH, 155°C. 24 h
+ Cl 77%
Lee, G.M.; Weinreb.
S.w.I. Org. Chem.. 1990, 55, 1281.
Rozen.;Hebel. D. J. Org. Chem., 1990, 55, 2621
8%
Section 369
Halide - Ketone
4
493
1. MeOTf , TiC14, ether 2. 1.8-bis-(dimethylamino)- w
C+
Cl+
naphthalene, MeCN 3. H30' Welch. J.T,; De Corte, B.; De Kimpe, N. J. Org. Chem., 1990, 55, 4981. 1. SOC12, CHZCI~, RT , 1 h
2.50% aq. H2SO4,6 h * reflux
& c1
w; Brunet, P. Synthesis, 1990, 595.
35%
81%
Barluenga, J.; Llavona, L.; Yus, M.; ConceI16n, J.M. Synthesis, 1990, 1003. mCPBA , HCI , DMF
OH
Me
PhJ
25"C, 6 h
*
P h L C I
80%
Kim, H.J.; Kim, H.R.; Byu. E.K, Synfh. Cornrum., 1990, 20, 1625.
\ I
Me0-Me
CuClrDMSO 1 h dioxane,reflux
~
0 Sahasrabhuddhe, AS.; B i v a . B.Llnd. J. Chem., 1990, 298, 61.
0
TsS02NC12, MeCN
P h T
40°C. 1.5 h
*
P h x , ,
80%
Kim.;Lee, I S . ; Lim, S.C. Chem. Letf., 1990, 1125.
J
1. LiBr , CICI-121,-78°C 2. 1.6 eq. MeLi ,-78°C
qpl
* 64% 3. HCI- ether 4. HCI - H 2 0 0 Barluenea. JJ Llavona, L.; Concellh, J.M. J. Chen. Soc., Perkin Trans I, 1990, 417. CO,Et
494
Compendium of Organic Synthetic Methods, Vo18
COzEt
Section 369
4
1 . 2 eq. BrCH2CI Br2CH2
2 . 2 eq. LDA , -78°C 83% 3. Me2CuLi c1 4. aq. HCI , 0°C Barluenga, J.; Llavona, L.; Yus, M.; Concellbn, J.M.J. Chem. Soc., Perkin Trans. I, 1991, 2890. PhiCl2 ,CH2C12
0
I ’ h w Ph 54%
0
c1
Moskovkina, T.V.; Vysotskii, V.I. Zhur. Org. Khint., 1991, 27, 717. 1. LDA 2. F-N(S02Ph)2, THF
J
q
+
Ph
. . R&x&g&.~.;
PhI(OAc)z, I2 cyclohexane hv (sunlamp)
*
@
Tetrahedron Lett., 1991, 32, 1583.
a
s. F A ; Han, W. Tetrahedron Lett,, 1991, 32, 1631.
Br
KerdeSk-;.
h
85%
F
also for fluorination of Ar-H Ofner, H. SynLRlt, 1991. 187.
Me Ellwood, C.W.; l%&a&a&
p
1. BuLi , CuBr-DMS
2. TFAA
Basha, A. Tetrahedron Lett.. 1991, 32, 2003.
84%
78%
Halide - Ketone
Section 369
NBS , cat. AgBF4
HO
)-cz c--/
495
- *5 7040%
Angara, G.J.; McNelis, E. Tetm..dron Lett., 1991, 32, 2099.
OSiMe,
CU(NO~)~, MeCN , RT
Cort. A.D. J. Org. Chem., 1991. 56, 6708. TI ( S O ~ T O I,)MeCN ~
0
*
OTs Ph Ph Khanna, M.S.;Garg, C.P.;~QQQLRL Tetrahedron Lett., 1992, 33, 1495.
92%
FU.SynLerr, 1992, 393.
Khanna, M.S.; Garg, C.P.; b o o r .
94%
MeOH-NEt3, CHzClz Tetrahedron Lett., 1992, 33, 6021.
Raina, S.; Bhuniya, D.;
PhI(0H)OTs MeCN
h0-
0
T
-I-
)”))
s
O
A
0 91% Tuncav. A,; Dustman, J.A.; Fisher, G.; Tuncay, C.I.; Suslick, K.S.Tetrahedron Lett., 1992, 33, 7647. KI-KI03-H2S04,45h
PhYMe 0
86%
0 *
Okamoto, T.; Kakinami, T.; Nishimura, T.; Hermawan, T.; Jpn., 1992, 65, 1731. 1. [AgF/PhSeBr/ ))))))) ]
2.30% aq. H202
*
Bull. Chem. SOC.
bF 52%
Usuki, Y . ; Iwaoka, M.; l j x n ~ & A J Chem. Soc., Chem. Commun., 1992, 1148.
496
Compendium of Organic Synthetic Methods, Vol8
0
oxone, HCI , DMF
Ph- CE C-Me
Section 37 1
* P
25°C. 2 h
h v c1 c1
94%
Kim, K.K.; Kim, J.N.;Kim, K.M.; Kim, H.R.; Ryu, E.K. Chem. Lett., 1992, 603.
- NITRILE
SECTION 370: HALIDE, SULFONATE
N C I
p
Pd(PPh3)4, HMPA proton sponge, 65°C
NcK1 N COZPh
4. N C02Ph Mori. M,; Kubo, Y.; Ban, Y. Heterocycles, 1990, 31, 433.
Rodriguez, J.; Duldre. J-P. SynLett, 1991, 477.
SECTION 371: HALIDE, SULFONATE
10"
Me0
rn
- ALKENE
1 . PhSeCl , MeCN AgF , RT , 18 h
*
2.03 , CCl4 , -2°C ~~0 3. iPr2N€I,reflux 44% 16 h v. J.FLMatthhews, D.P.; Barney, C.L. TefrahedronLett., 1990, 31, 973. /
1 . Red-A1 , ether, 0°C
2.12, -78°C + 2 3 T , PhS- Cr C 7 OH 3. HoMOH * NaOzC
. .
COzK
lh
Ph 80%
Maeno!ls.;Doyle, T.J.; Kim, K.D. Tetrahedron Lett., 1990, 31, 2541.
Me H- CEC 4 . OTs
67%
C F ~ C UDMF ,
* F,CHG C: CHMe 65%
Burton.;Hartgraves, G.A.; Hsu, J. TefruhedronLen., 1990, 31, 3699.
Section 37 1
Halide - Alkene
H- CE C-
497
C & I + ~ ,DMSO
Br
20°C
* C6F13HC- C=CH, 75%
Huns. H-H, Tetrahedron Lett., 1990, 31, 3703.
Roush. W.R.; Moriarty, K.J.; Brown, B.B. Tetrahedron Lett., 1990, 31, 6509.
Ph- CE C- H
IPy2 BF4, AcOH CH2C12, HBF4
*
12h
Ph
AcO'
53%
Barluenga.;RodHguez, M.A.; Campos, P.J. J. Org. Chem., 1990, 55, 3104. b h m g d . ; Rodriquez, M.A.; C a m p s , P.J. Tetrahedron Lett., 1990, 31, 2751. Cmpos, P.J.; Lbpez, F.; Llorente, I.; Rodriguez, M.A. Tetrahedron Lett., 1990, 31, 7375. BarluenPa.;Rodriguez, M.A.; Gonzhlez, J.M.; Camps, P.J. Tetrahedron Lett., 1990, 31, 4207.
u; F,C
1
OEt
Thenappan, A.;
F
1. Dibal ,THF b
2. (E(O)~POCFCO~CO~EL Li CO2Et -78°C - +25"C 63% (83:17 E:Z) D.J. .I. Org. Chem., 1990, 55,4639.
m.
F ~ C O ~ T Ml.LDA P
SiMe,
2. PhCHO
CO*TMP 49%
TMP = 2,4,6-lrimethylphenyI
(1:29 E:Z) Welch.: Herbert, R.W. J. Org. Chem., 1990, 55, 4782.
1. KHMDS , -100°C (33212
n-C6H13
1
4
2. PhOIS-qLi B
(84:16
n-C6H13
E:Z)
Chmeau, P.; Julia, M.; Verpeaux, J.N. Bull. SOC. Chim. Fr., 1990, 127, 275.
OBr
'' Br Bandodakar, B.S.; -Synthesis,
morpholine ,DMSO , 8 5 T KOH,EtOH
1990, 843.
66%
eBr 80%
498
Compendium of Organic Synthetic Methods, Vol 8
Section 37 1
CBrC13,2 eq. VCl2 DMF , 80°C, 20 h
c
C
c
l
3 63%
Hirao, T.; Ohshiro, Y. SynLett, 1990, 217.
Bu- Cr C-Et
Me3SiCI , Nal , MeCN O.SHzO.RT, 1 h Ic
Bu)=;l Et I
Kamiya, N.; Chikami, Y.; Jshii. Y. Syntett, 1990, 675.
-
>98%
- dCF* qxF2
1. AIC13, 150°C , 3 d 2. 2 eq. Zn ,DMF
CF3CFBrCF2Br 3. lriglyrne , 25OC. 48 h c1
Morken, P.A.; Lu, H.; Nakamura, A.;
F,C- CH,
+
Tetrahedron Lett., 1991, 32, 4271.
1. sec-BuLi 2. n-C,H,3CHO
n-C6H 1 3
3. DAST ,CH2C12
b
C
CF3
DAST = diethylaminosulfur trifluoride
50-60%
Tellier, F.; SauvStre, R. Tetrahedron Lett., 1991, 32, 5963.
j
0 O M OMee
SiMe
,CH2C12
SnBr2-AcBr , RT , 1 h
Orivama. T.; Iwanami, K.; Tsukamoto, K.; Ichimura, Y.; Koga, G. Bull. Chem. Soc. Jpn., 1991, 64, 1410. 4 eq. M0C15,24 h
c1
34%
brae. T.; Nagata, S.; Yamaguchi, M.; O s h i r o . B u l l . Chem. Soc. Jpn., 1991. 64, 1717.
CHO
(CF$0)20 , Zn-Cu , MS CF3CC12C02Me. THF 60°C
=
m F : 0 2 " " 88% (65:35
Allmendinger. T,; Lang, R.W. Tetrahedron Lett., 1991, 32, 339.
ZE)
Halide - Alkene
Section 37 1
0.33 benzene PhCSAICI - CHg12,O°C
499
*% /
44%
wMe
c.., L.
Bhaskar Ready, G.;Hanamoto, T.; Hivama. T. Tetrahedron Lett., 1991, 32, 521.
Ph
Me3SiC1, NaI MeCN
OAc
*
50%
Me
Amouroux. R,;Ejjiyar, S . Tetrahedron Lem., 1991, 32, 3059.
4CF3 TMEDA ZnBr
.r
-
cat. Pd(PPh3)4, THF
96%
UB.; XLLY.J. Org. C h e w 1991, 56, 7336. a; &LX, Tetrahedron Lett., 1992, 33, Sll[coupling of two vinyl halides]. H- Cr C-C02Et
Lil ,AcOH ,MeCN
*
I
reflux, 21 h
c02Et 87%
Ma, S.; U; Li. 2.J. Org. Chern., 1992, 57, 709. Ma, S.; Tetrahedron Lett., 1990, 31, 7653. Ma, S.; U J . Chern. Soc., Chern. Commun., 1990, 1643 [with LiBr]. MegSi- C: Cf
Me Me CI
TiC14, CH2Clz
*
H Me MuL&H.; Bguml, E.; Cibura, G.; Koschinsky, R. .I. Org. Chern., 1992, 57, 768. 4.2 eq. 1 2 , RT ,24 h
Me
*
&I
Me
57%
Johnson.;Adams, J.P.; Braun, M.P.; Senanayake, C.B.W.; Wovkulich, P.M.; UskokoviC, M.R. Tetrahedron Lett., 1992, 33, 917.
Compendium of Organic Synthetic Methods, Vol8
500
1. TfzO, CHzC12
-CHO
fl'' >
Section 37 1
-1
0°C. 12 h 2647% 2. MgIz (96:4 E Z ) 3. DBU Martinez.;Alvarez, R.M.; GonzAlez, S.M.; Subramanian, L.R.; Conrad, M. Tetrahedron Lett., 1992, 33, 2043. 1 . 2 eq. BuLi , THF 2. B B u ~LiF ,
90% 3. CuI ,THF-HMPA Ph 4. 2% Pdz(dba)3-PPh3 PhI,RT,lh Ichikawa. J,: Minami, T.; Sonoda, T.; Kobayashi, H. Tetrahedron Lett., 2992,33,3779.
CF3CHzoTs
no
1. LDA
t-Bu
t
t-Bu
2. " i n N
0"' 87%
NTfi
-78"C, 2h Comins. D.L,;Dehghani, A. Tetrahedron Lett., 1992. 33, 6299. Bu3SnSnBuj, hv (sunlamp)
SPh
oI
, PhH , 3 0 min
Cuman. D.P,; Yoo, B. Tetrahedron Lett., 1992, 33, 6931. POC13, DMF ,RT ClCHCC12 , 3 d
Cbz Al-awar. R.S.; Joseph, S.P.; Comins.
3
96%
Cbz D L Tetrahedron Lett., 1992, 33, 7635.
1. thexylBHz , THF 2. (MezN)3P=O t n-C4Hg-C=C-H C U C I ~HzO/THF , Bu 3.20"C + 70°C Masuda. Y,;Hoshi, M.; Arase, A. J. Chem. SOC.,Perkin Trans. 1, 1992, 2725.
+
c1
72%
Ketone - Ketone
Section 372
501
5%
49% (1:9 E:Z)
Albrecht, U.; Warthow, R.; Hoffmann, H.M.R. Angew. Chem. Int Ed. Engl., 1992, 31, 910. AgBF4, AIC13, 10 min microwaves (650 W)
. . Vlllemln.; Labiad. B. Synth. Commun., 1992, 22, 2043. CFS , MeOH
€
'
h
e SnMe3
t
P
h
o
F
48%
CFS = cesium fluoroxysulfate Hodson, H.F.; Madge, D.J.;
SynLetl, 1992, 831.
SECTION 372: KETONE
-
KETONE
-L
hv (Hg lamp) ,2.S h
Ni(II)/Co(II) filter
0
2S°C ,air
95%
0
Macias, F.A.; Molinillo, J.M.G.; Collado, I.G.; Massanet, G.M.; Rodriquez-Luis, F. Tetrahedron Lett., 1990, 31, 3063.
0
2 0
0
,FeCb ,2O"C
claynick, 24 h %?
claynick = [K-10 montrmorillonite/NiBr/MeCN/280°C]
Laszb.;Montaufier,
M-T.; Randriamahefa, S.L. Tetrahedron Lett., 1990, 31,4867. 0
SePh
hv (100 W Hg m l :)
PhH , RT, 3 h
Watanabe, Y.; Yoneda, T.; Ueno, Y.; Tom T, Tetrahedron Lett., 1990, 31, 6669.
Compendium of Organic Synthetic Methods, Vol 8
502
Section 372
LDA ,THF ,25"C, 6 h
Gu, X-P.; Kirito, Y.; Ikeda, 1.;
Ph
J. Org. Chem., 1990, 55, 3390.
il
-
ECHO, SnC12 CH2C12, RT
CHN2
0
Ph
0
JUL88%
Padwa.;Hornbuckle, S.F.; Zhang, 2.; Zhi, L. J. Org. Chern., 1990, 55, 5297. C02Me v C 0 2 t - B ~ c s 2 c o 3 , CIiC13 0 2. PTSA
@ J 0
73%
Me
Ruel, K.;Hogan, K.T.; Deslongchamos.SynLeii, 1990, 516. OSnBu, dMeRT, 1.HMPT h
M
0
e
0
d
p
h
+ M 0e m Ph o 12%
13%
Baba.;Yasuda, M.; Yano, K.; Shibata, I.; Mahuda, H. J. Chem. Soc., Perkin Trans. I, 1990, 3205.
*
Me
NO2
0-Li+ 1. =( ,THF,-78"C Bu
2.10% HCI , RT , 5 h
Miyashita, M.; Awen, B.Z.E.;
.
.
OSiMe3 P h W B F 3
-
BudM 65%
0
Synthesis, 1990, 563.
*
-78°C -+ -10°C
74%
Zefirov, N.S.; Samoniya, N.Sh.; Jutateladze, T.G.; Zhdankin, V.V. Zhur. Org. Khim., 1991, 27, 220 (Engl., p. 194).
503
Ketone - Ketone
Section 372
PdC12(MeCN)2
OC""
cs c-
H 2 0 , THF , RT
n-C6H13
-
&GH13 63%
Mahrwald, R.; Schick. H.Angew. Chem. Inr. Ed. EngL, 1991, 30,593. OSiMe7t-Bu
=.(
Ph
IDMF
Ph30H 2.4 eq. Mn(pic)3
80%
Ph
0°C Mn(pic)3 = manganese (111) 2-pyridinecarboxylate Iwasawa, N.; Hayakawa, S.; Isobe, K.; Narasaka.Chern. Leff., 1991, 1193. 12, DMSO , 155°C. 10 h
Ph+
Ph
p h q P h
85%
0 Yusybov, M.S.; m o v . V.D. Synthesis, 1991, 131.
2
kC02Et
l.Na,ether 2. SOCl;1, - 1 8 T -+ RT
Olah.;Wu, A. Synfhesis, 1991, 1177.
0
French. L.G,; Fenlon, E.E.; Charlton. T.P. Tetrahedron Left.. 1991, 32, 851.
,CsHC03, MeOH 2OoC, 2 h 2.4N Ii2SO4,6ODC,4 h 3. 3MsCl,5NEt3 cat. DMAP , CH2C12 20"C, 30 min P ' A n c e l d ; Gomez-Pardo, D. Tetrahedron Leff.,1991, 32, 3063.
24% overall
504
Compendium of Organic Synthetic Methods, Vol 8
0
1 . e- , SmCl3 , Mg anode
P h h P h 0
2.H30t
PhC02Me
Section 372
68%
Htbri, H.; Duaach. EL Heintz, M.; Troupei, M.; Ptrichon, J. SynLetf, 1991,901.
P
h
q Ph 0 83%
Olah. G.A.; Wu, A. J. Org. Cheni., 1991, 56, 902.
2 eq. BuLi , -110OC
-CO2Me
* Bu
0 Sevferth.;Weinstein, R.M.; Hui, R.C.; Wang, W-L.; Archer, C.M. .I. Org. Chem., 1991, 56, 5768.
HO
)-c: c
Me
cB-Br, PhCHO
Me
PhH , RT , 1 d
62%
0
Br
Shimizu, H.; Hara, S.; Suzuki. A,Synrh. Commun., 1990, 20, 540. 1 . BuLi , BF3*OEt,
PhSo2Me
2- O P nC,H1, 3. Jones oxidation 4. DBU
L.
Marczak, S.; W i c h a . S y n t h . Cornmun., 1990, 20, 1511.
>n-C5Hll
0
60%
5 14
Compendium of Organic Synthetic Methods, Vol 8
Section 314
1. TMSCl , NEt3 2. Pb(OAc)z, MeCN
benzoquinone
52%
Kim, M.; Applegate, L.A.; Park, 0-S.; Vasudevan, S.; W a t t . S y n t h . Commun., Z990, 20, 985.
Fph
H-CS-CHzOMe CH2C12,4 h
Rf2(pfb)4 syring pump addition
N2
Ph
Me0 (82
pfb = perfluorobutyrate
OMe
0
80%
18)
Dole, M.P.; Bagheri, V.; Claxton, E.E. J. Chem. SOC.,Chem. Commun., 1990, 46. NO2
30%MeCN H202,3N , 7OoC, HCI3 h
*
dMe 72%
0
Gupta, K.B.; Franck, R.W. SynLett, 1990, 355.
Me3Si0
OSiMe3 Me
Pelerson.;Kirchhoff, E.W. H
PhCHO , TiC14, -78°C CH2C12 , 4 h
66%
Ph SynLett, 1990, 394.
1. TMSOTf 2. T i c 4 3. Pb(OAc)4
0
Me
&
Me0
Ls.T.V.; Porter, J.R.; Roden, F.S.Tetrahedron, 1991, 47, 139.
48%
Section 314
Ketone - Alkene
SnBu-,
515
Q
Bu3SnH , AIBN PhH ,reflux
77%
Baldwin. J.E.; Adlington, R.M.; Robertson, J. Tetrahedron, 1991, 47, 6795. Me1 , CO (1 atrn) , 4OoC Mnz(C0)lo. CTAB+
n-C5H 1\= 1 C=
+
a-(%H$
CH2Cl2, NaOH 40% CTAB = cetyltrirnethylammoniombromide Satyanarayana, N.; A~QuJLJ. Chem. Soc., Cheni. Cownun., 1991, 8.
OH Me0
MMP , MeCN , 2 0 ° C , 1 h cat. Fe"' (TF4PS4P)
0
~
pH 3 (tartrate buffer)
OMe
7%
85%
Me0
MMP = magnesium monapemxyphthalate Fe (TF4PS4P) = iron-rneso-tetrakis(2,3,5,6-tc~afluorophenyl) tetrasulfonatoporphyrin
0
Artaud, I.; Aziza, K.B.; Chopard, C.; Mansuy, D. .I. Chern. Soc.. Chem. Conimun., 1991, 31.
Me3Si
SiMe3
0
1. BzCI-AlCh , 0°C CHZC1, 2. C-,H,5COCI-AICI, * Ph CHZCI,, O°C -+ RT
0
55%
Babudri, F.; Fiandanese, V.; Marchese, G.; Naw. F. .I. Chem. Soc., Chern. Corrtmun., 1991,
237.
H
O
G OH
BnMe3N Br3, NaOAc CH2C12, RT quant.
Qiieaeshi. &; Morikawa, Y.; Fujisaki, S.; Kakinami, T.; Nishihara, K. Bull. Chern. Soc. Jpn.. 1991, 64, 336.
0
PhCliO , In1 , THF #
Ph
Br
PhLPh
Araki. SJ Butsugan, Y . Bull. Chern. Soc. .Ipn., 1991, 64, 727.
74%
Compendium of Organic Synthetic Methods, Vol8
516
Section 314
(c'B-n-C8H17 Bu4
w
I
CO , Pd(PPh3)4,25"C dioxane , K3P04
Ishiyama, T.; Miyaura, N.; n-C5H117_
csc'
B,,
OMe Fukuda, Y.;
'
98%
Bull. Chem. SOC. Jpn., 1991, 64, 1999.
10%H20 in MeOH 5% NaAuC104 c
0 n-C5H1 bI
reflux, 2 h
B
u
79%
Bull. Chem. SOC.Jpn., 1991, 64, 2013.
bMe PhCHO
TMSOTf
06Me 67%
Sato.;Hayase, K. Bull. Cheni. SOC.Jpn., 1991, 64, 3384.
Honda.;Ishige, H.; Tsubuki, M.; Naito. K.; Suzuki, Y. J. Chem. Soc., Perkin Trans. I, 1991, 954.
JCrafft. M.E.; Juliano, C.A.; Scott, 1.L.; Wright, C.; McEachin, M.D. J. Am. Chem. Soc., 1991, 113, 1693.
02
OSiMe3
Pd(2-furyl)$12 , xylene reflux , 3 6 h
Hetuick, C.M.; Scott. W.J. J. Am. Chem. SOC., 1991, 113, 4903.
Ketone - Alkene
Section 374
Ph
0
Ph -
>Me
0
517
,DMF
0 I-ph BF4 Cat. Pd(OAc12, RT
-
\Me
73%
NaHC03
0 Moriartv.;Epa, W.R.; Awasthi, A.K. J. Am. Chem. SOC.,1991, 113, 6315. 1. t-BuCOS02F , CHK12
-70°C
2. NEt3 0 Gavrishova, T.I.; Shastin, A.V.; Balenkova, E.S. Zhur. Org. Khim., 1991, 27, 673 (Engl., p. 580).
.
Q
1. BuLi THF 2. PhCN ,-78T 4 -5OC
OEt
3' M e 0 0 CHO, -5°C +*RT
E~O-P-Me
86%
OMe
4.5N H2S04 , RT , 1 h
Lee, K.; Dh. D.Y, Synthesis, 1991, 213.
K
MqSn
Degl'Innocenti, A.;
SnMq
0 THF, reflux, 2 h 2. PdBnCl(PPh& O°C 4 RT .2h
m;
n Me C:C,fMe
*
-t).o
0
; Ricci, A.; Seconi, G. Synthesis, 1991, 267.
n-Bu-1 ,THF -78°C + -35°C
OMe
n
. . Maletlch.; Leigh, A.J.; Condon, S. Tetrahedron Lett., 1991, 32, 605. . . -G.;
65%
n-C4H9 61%
Leigh, A.J. Tetrahedron Lett., 1991, 32, 609.
0.016M , 1M LiBF4 12 h , 25°C
0 Smith.;Houk, K.N.Tetrahedron Leu., Z991, 32. 1549.
quant.
Compendium of Organic Synthetic Methods, Vo18
518
' 0
A C 0 2 M e
Section 374
ECHO , COCI~ AczO ,MeCN 25"C,8h
Iabal.;Srivastava. R.R. Tetrahedron Lett., 1991, 32, 1663. CHO
LDA , TMSCl -78"C-+ RT 98 % Herscovici.;Bournaim, L.; Antonakis, K. Tetrahedron Lett., 1991, 32. 1791.
Ph
OEt
0
Po)
)LC 0 2 Et 6
PhCN
*
P
h
,24h
3 SOsNa
97%
4 CO2Et
Pd(dha)z Safi, M.; ~ Q L Q . Tetrahedron Len., 1991, 32, 2025.
10% CpRuCl(PPh3)z dioxane ,reflux , 1 h
Ph
* A Ph
Tray.B.M.; Kulawiec, R.J.Tetrahedron Letr., 1991, 32, 3039.
k% 74%
5% Pd(PPh)3)4, reflux, 1 h THF* Ph
Ph
E m . S,; Uh, K.H.; Lee, S.;Park, J.H. Tetrahedron Lett., 1991, 32, 3395.
1. EtAIC12, PhMe
2. aq. NH&I
Me
.-
c
Me
44%
Me
. . m; Hull, K.; Casares, A.M.; Khetani, V . J. Org. Chem., 1991, 56, 3958.
23%
Ketone - Alkene
Section 314
Php
A O A c
OH
519
,THF
Ru(C0)3(PPh3)2 , 12 'h K2CO3 ,150"C CO (10 Kg/cm2)
2Mi
Ph 76%
J, Org. Chem., 1991, 56, 487.
Kondo, T.; Mukai, T.;
LDA , THF , HMPA
+
0
&Me Me
61%
Mathew. J, J. Org. Chem., 1991, 56, 713. =ISnBu',THF,8O0C
&o
Pd(PPh314, LiBr 36 h
69%
Hettrick, C.M.; Kling, J.K.;Scott. W.J. .f. Org. Chem., 1991, 56, 1489.
NaOMe ,MeOH
fi
Me0
e- ,C anode, 13 F h o l stainless steel cathode =-
OMe
55%
M e 0 OMe Barba.;Chinchilla, R.; Gbmez, C. .I. Org. Chem., 1991, 56, 3673. 1. PhLi
2. aq. NH&l
do
3. 138°C
t-BuO
0
4.AgzO,K2C03
0
Heerding, J.M.; Moore. H.W,.I. Org. Chem., 1991, 56, 4048. 1. MeO2CCSC02Me , PhH 110"DC.2 h
b
Me,SiO
2. aq. H+
63%
' t-BuO
fi
C02Me
0
67%
C02Me
Thiemann, T.; Kohlstruk, S.; Schw*, G.; Pe Meiiere. A, Tetrahedron Lett., 199Z, 32, 3483.
Compendium of Organic Synthetic Methods, Vol8
520
Ph
Ph
H
"KO0
Section 374
1. PdCb(PhCN)2 2 eq. NEt3 NaCH ( C 4 M e ) t
2. co 3.
gc)@ 6 &....
Masters, J.J.;
SnMq
m; Tamariz, J. J. Org. Chem, 1991, 56, 5666. Cu(0Ac)z. 2 eq. Mn(OAc)3 AcOH
50%
18%
Snider.;Memtt, J.E. Tetrahedron, 1991, 47, 8663.
Me
hv ,CH2C12, EtI
SnMe3
-
*TGsph
Sato,;Takezoe, K. Tetrahedron Lett., 1991, 32,4003.
SPh OAc
Kudo, K.;
4311.
OSiMq
+
10%MegiOTf, CH2C12
-78OC --t RT
a; Hashimolo, Y.; Houchigai, H.; Hasegawa, M. Tetrahedron Lett., 1991, 32, (94
6)
1 . M g , THF 2. MeGnCl
<si~,,
3. AcCl , CHC13.1; 2% BnPd(PPh3)zCl 65OC
SiMe, 81%
Lane K-TJ Kim, S.S.; Lee, J.C. Tetrahedron Lett., 1991, 32, 4341. (BuCH=CH)2Zn, THF-DMF PdC12(PPh,)2 , 2 BuLi
87%
Neglshi.; Owczaczyk, Z.R.; Swanson, D.R. Tetrahedron Lett., 1991, 32, 4453.
688
’30)
Ketone - Alkene
Section 374
52 1
0
1.
p&Br
t-BuOK, THF , RT
CO2Et
2.2M HCIICH2CIz
RT
COzEt
*
82%
Ph
Hatanaka. M,; Himeda, Y.; Ueda. 1. Tetrahedron Lett., 1991,32,4521.
2. MeOH
hq,tI( +
0
C02Me
17%
57% J&Q. C-C,; Wei, C-P. Tetrahedron Lett., 1991, 32, 4553.
20%Cut, NMP air, benzoquinone
Me
0
Me
c
SnBu,
Liebeskind. L.&; Riesinger, S.W. Tetrahedron Lett., 1991, 32, 5681. 1 . 2 eq. Mg , THF 2. CuBreSMe2 0
0
Me
8WO
c
, -30°C
65°C
CI
Canonne. P,;Boulanger, R.;Angers, P. Tetrahedron Lett., 1991, 32, 5861.
aO O , , ~ ~ -- -.
I
Q
2 eq. CHzC12 KzCOJ.0.2 NaI
r-BuMe2Sid t-BuMe,SiO Larock.; Lee, N.H. Tetrahedron Lett., 1991. 32, 591 1 .
.
n- C5H1 1
0
62%
522
Compendium of Organic Synthetic Methods, Vol 8
Ph0,S
'd
Leon, F.M.; Carretero.
1.
0
,35h
Section 374
*
2. NaOEt ,EtOH ,0°C 25 min
91%
Tetrahedron Lett., 1991, 32, 5405.
&
PhSSPh , AIBN , hv
Tile &
Kim.;Lee, S . Tetrahedron Lett., 1991, 32, 6575. QSiMe,
snC14, Ck12C12 -70°C + -23":
Me0 Johnson,T.O.; i
/Lcsc
82%
,, OMe 68%
(6:l dr)
k a m ~ UTetrahedron , Lett., 1991, 32, 7361.
1'I
CHO
'
1
B
c
MeCN , piperidine ,RT
u
p S02Ph
OH
79%
oO"
Trost. B . W ; Grese, T.A. .I Org. . Chetn., 1991, 56, 3189. rnontlnorillonite , 15 h
TolS02NaI Hfllacetnne PhH , RT
-
75%
"'S0,Tol
Biswas, G.K.; Bhattachaw. !a. P. Synfh. Commun., 1991, 21, 569.
Compendium of Orgbnic Synthetic Methods, Vo18
542
Section 380
Solladie.;Colobert, F.; Ruiz, P.; Hamdouch, C.; Carrello, M.C.; Garcfa Ruano, J.L. Tetrahedron Lett., 1991, 32, 3695.
OH
-/
OAc
Ph0,S
46% (>98% ee ,S)
(>95% ee , R) . ;Femhdez-Mayoralas, A.; Conde, S. Tetrahedron Lett., 1991,
Dominguez, E.; 32, 5159.
p$ 0
+ P h O 47% , S y
PhQS*
. t
0,
QAc
OH
.
, iPnO.5.5 h
1. NaHDMS ,0°C 2. PhCHO ,0°C
3. HCI, EtOH
Ph
-
0
0 (96
4)
87%
Aggmval. V . L ; Franklin, R.J.; Rice, M.J. Tetrahedron Lett., 1991, 32, 7743.
0
7'1 Ph
1. LDA , THF , -78°C 2. iPrCHO , -78°C , 5 min
OH
3.H30'
Bn
Bn
1)
(4
Caset.;Muxhejee, I.; Trabsa, H. Tetrahedron Lett., 1992, 33, 127. OH
Zn(BH4)2, DME
* &NO2
5 min
Ranu.; Das, A.R. Tetrahedron Lett., 1992, 33, 2363.
73%
(40:60)
!?
EtO.y-CH,/BuLi,THF OEI
fh
-78°C
2. BF3*OEt2 , -70°C 2h
Racha, S.; Li, Z . ; El-Subbagh, H.;
*
Q
EtO-P-ph OEt
OH quant.
Tetrahedron Lett., 1992, 33, 5491.
90%
543
Oxide - Amide
Section 382
SECTION 381: OXIDES
- ALDEHYDES
9 do?- OMe
1.
0 0-f- ()Me OMe CHO
,acetone/CH2Clz
-10°C 20"C, 2 h 2.RT. 1 2 h
OMe
n-C5H1 1
>c8
n-CSH1ly 99%
Adam. W.; Hadjiarapoglou, L.; Klicic, J. Terrahedron Lett., 1990, 32,6517. 1. CHz=N-NMez CHZC12, RT 2.03
yNo2
-
OZNyCH0
74%
3. DMS Cassaletta. J-M,; FemAndez, R. Tetrahedron Lett., 1992, 33, 3691.
SECTION 382: OXIDES
MeS
f
- AMIDES 1. MeCN, 30°C
OZ
.cN.,, 4 NO2
2. Hg+2,aq. MeCN 30°C
SMe
>70%
treatment wih NazS led to thioamides Manjunatha, S.G.; Reddy, K.V.; & .& ap
CbzHN ,-
J+COzH
S. Tetrahedron Lett., 1990, 31, 1327.
1. Pb(0Ac)d , DMF 2. P(OMe)3 , Tic14
CbzHN
&OMe
P,
0 OMe 76%
Green, 1.M Tetrahedron Lett., 1990, 31,6827. 1. BnNH2, 30"C, THF, 18 h 2. NEt3 , THF , 19 h Pb-cz c q c , , NO,
3. t-BuOH ,THF ,30"C cat. Triton B , 4 8 h
t
0
Bn
49%
Patra R.; Maiti, S.B.; Uumje~A ;Chakravarty, A.K. Tetrahedron Lett., 1991, 32, 1363.
Compendium of Organic Synthetic Methods, Vol8
544
Me
*N-Ph
NO, 3 eq. Et3SiH , DCE 5% Co (salen) derivative
Me
ON
RT
0
Section 383
77%
0
Kato, K.; Mukaiyama, T. Chern. Lett., 1990, 1395.
0N CH,
To1 1. LDA, e
2. LDA , CH2=CHC02Me
Hua. D.H.; Bhafathi, S.N.; Panangadan, J.A.K.; Tsujimolo, A.
S02Ph
Bn
N=\/\,OBn
+
(0
cop
Green, D.L.C.; -C.M.
,i.Org. Chern., 1991, 56, 6998.
CoB S O2Ph
B F,*OEt, THF, -78°C
76%
0
Tetrahedron Lett., 1991, 32, 5051.
SECTION 383: OXIDES
- AMINES 1. (CHZO),
NaOMe 2. P(OMe),
0.OMe
H rP\
Tic14
Ha.;Nam, G-S.; Park, K.P. Tetrahedron Lett., 1990, 31, 1567. N S
DBU ,o-xylene reflux, 18 h
'@
oo
79%
Chucholowski, A.W.; Uhlendorf, S. Tetrahedron Lett., 1990, 31, 1949.
phQsx
1 . BnNH2 , CH$&/MeOH 2. NaOMe
PhQS
*
Padwa. A, ; Norman, B.H. J. Org. Chern., 1990, 55, 4801.
rrPh J !
Bn
quant
Oxide - Amine
Section 383
0
i,,,N H M ~1. BuLi, THF
Me' \
PhHN
*g
____c
2. ECH=NPh
Ph
545
PhHN Et
+
-
(94 Dikic, B. Tetrahedron Lett., 1990, 31, 5231.
&RLS&;
6)
68%
- Q-0
TolS02CH2CI Bu3SnHI AIBN
n
Ph
H MeHN
MeHN
GNU0
PhH , reflux
54%
S02T0l
(84:16 cis:trans) Renaud.; Schubert, S.Angew. Chem. Int. Ed. Engl, 1990, 29,433. **#.
p
To1°'s4
Me NHBn
L-Selectride ,CH2Ci2 -20°C , 6 h
57%
Tol'
Qeura.;Tomori, H.; Fujita, M. Chem. Lett., 1991, 1407.
(97:3 RR:RS)
Bn
Bn
I. LDA , THF , -78°C 2. BnBr
Bu
Bu
(34 Bell, S.I.; Parvez, M.; p J. Org. Chem., 1991, 56, 373.
PhO,S Ph
N - H ,25"C
SO2Ph
c
66)
qih
96%
!)o%
SOZPh
W w a . A.; Gareau, Y.; Harrison, B.; Norman, B.H. J. Org. Chem., 1991, 56, 2713. N O 2 . 0 3 ,