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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@
1995 by John Wiley & Sons, Inc.
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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-
<
X
Miscellaneouscompounds 15 5
Alkenes
Nitriles
Ketones 12 4
Hydrtdes (RH)
27 13 28 13 29 14 30 14
39 30 40 35 41 36 42 39 43 45 44 45 45 47
24 11 25 11
Ethers, epoxides
Halldes,sulfonates.sulfates 10 3
38 29
32 16 33 18 34 18 35 28 36 29
23 10
7 3
16 6 17 6 18 7 19 8 20 9 21 9
Esters
Amines
Amides
Aldehydes 4 2 Alkyls, methybnes, aryls
Alkynes
1 1 Carboxylicacids 2 acid halides,anhydrides 2 Alcohols, phenols
54 61 55 61 56 62 57 63 58 63 59 63 60 64
47 54 48 54 49 58 50 58 51 59 52 59 53 60 69 71 70 72 71 78 72 79 73 80 74 81 75 116
67 70 68 70
61 66 62 67 63 68 64 69 65 69
85 132 86 133 87 133 88 134 89 135 90 136
96 142 97 144 98 153
81 120 82 127 83 131 99 153 100 153 101 155 102 155 103 157 104 158 105 159
91 139 92 139 93 140 94 140
76 117 77 117 78 119 79 119
114 176 115 177 116 178 117 179 118 182 119 182 120 183
111 173 112 174 113 174
106 166 107 166 108 168 109 172
134 194 135 198
132 193
129 189 130 191
127 188 128 188
123 184 124 186
121 184
149 207
145 203 146 205 147 207
142 202 143 203
138 200 139 201
165 219
162 218 163 219
157 213 158 213 159 214 160 215
152 210 153 210 154 212
166 220 167 220 168 183 222 242 169 184 225 242 170 227 171 186 227 243 172 187 228 243 173 229 174 189 230 244 175 190 231 244 176 191 233 244 177 234 178 193 237 245 179 237 180 195 238 245 209 261 210 264
225 273
196 247 197 212 251 267 198 213 251 267 199 214 252 267 200 253 201 254 202 217 254 268 203 255 204 219 255 269 205 220 256 272 206 221 258 272 207 222 259 273
30A 45A 60A 90A 105A 180A
Sect.
138 163 239
€4
Pg. 14 48
Blanks in the table correspond to sections for which no additional examples were found in the literature.
Carboxylic acids Alcohols, phenols Aldehydes Amides Amines Ketones
PROTECTION j
INDEX, MONOFUNCTIONAL COMPOUNDS
2.
290 316 291 317 292
292 319 292 320 293
322 294
279 305 279 306 280
281 308 282 309 283
311 284 378 540
368 338 369 339 370
341 371 381 543
348 332 352 380 540
365 335 366 336 367
328 329 336 330 340
318
306 326 309 327
294
414 356 414 383 544
405 353 408 354 409
380 346 382 347 383 386 349 386 382 543
350 396 351 398
375 343 376 344 377
444 362 444 3114 547
427 359 432 360 437
357 424
474 367 475 385 548
461 364 463 365 465 496 371 496 386 549
368 490 369 492 506 374 506 387 550
372 501 529 376 529 388 553
377 531 389 390 553 559
Blanks in the table correspond to sections for which no additional examples were found in the literature.
288
277
/
Sections-heavy type Pages-light type
INDEX, DIFUNCTIONAL COMPOUNDS
INTRODUCTION Relationship between Volume 8 and Previous Volumes. Compendium of Organic Synthetic Methods, Volume 8, presents about 1400 examples of published reactions for the preparation of monofunctional compounds, updating the 9250 in Volumes 1-7. Volume 8 contains about 1640examples of reactions which prepare difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 8 adds atmost 60 pertinent reviews in the various sections. It is interesting that Volume 8 contains approximately 1200 more entries than Volume 7 for an identical three-year period. One or two important new journals appear (such asSynLett), but the most dramatic increase was in reactionsthat prepared difunctional compounds. This increase in reactions led me to “compress” the format of the Compendium somewhat, in an attempt to keep the length of the manuscript in line with previous volumes. Chapters 1-14 continue as in Volumes 1-7, as does Chapter 15, introduced in Volume 6. Difunctional compounds appear in Chapter 16, as in Volumes 6 and 7. The sectionson oxides as part of difunctional compounds, introduced in Volume7, continuein Chapter 16of Volume8withSection 378 (Oxides-Alkynes) through Section 390 (Oxides-Oxides). Following Chapter 16 is acomplete alphabetical listing of all authors (last name, initials). The authors for egch citation appear below the reaction. The principle author is indicated by underlining (Le., Kwon, T. W.; Smith, M. B.), as in Volume 7. Classification and Organization of Reactions Forming Monofunctionai Compounds. Chemical transformations are classified according to the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section, reactions are loosely arranged in ascending order of year cited (1990-1992), although an effort has been made to put similar reactions together when possible. Review articles are collected at the end of each appropriate section. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation appearing in both starting material and product, or by increases or decreases in the length of carbon chains; for example, the reactionst-BuOH --* t-BuCOOH, PhCH20H -+ PhCOOH, and PhCH=CHCH20H --+ PhCH= CHCOOH would all be considered as preparations of carboxylic acids from alcohols. Conjugate reduction and alkylation of unsaturated ketones, alxvii
xviii
INTRODUCTION
dehydes, esters, acids, and nitriles have been placed in Sections 74D and 74E (Alkyls from Alkenes), respectively. The terms hydrides, alkyls, and aryls classify compounds containing reacting hydrogens, alkyl groups, and aryl groups, respectively; for example, RCH2-H 3 RCH2COOH (carboxylic acids from hydrides), RMe --* RCOOH (carboxylic acids from alkyls), RPh -+ RCOOH (carboxylic acids from aryls). Note the distinction between R2C0--* R2CH2(methylenes from ketones) and RCOR' --* RH (hydrides from ketones). Alkylations involving additions across double bonds are found in Section 74 (Alkyls, Methylenes, and Aryls from Alkenes). The following examples illustrate the classification ofsome potentially confusing cases: RCH=CHCOOH + RCH'CH2 RCH=CH2 4 RCH"CHCO0H ArH ArCOOH ArH 3 ArOAc RCHO 3 RH RCH=CHCHO + RCH=CH2 RCHO -.* RCH3 R2CH2 4 R2CO RCH2COR + R2CHCOR RCH=CH* 4 RCH2CH3
+ HC=CH ROH + RCOOH
4
RCaX
-.*
RCOOR
RCHSHCHO
-.*
RCH2CH2CHO
RCH-CHCN
+
RCH2CH2CN
RBr
Hydrides from carboxylic acids Carboxylic acids from hydrides Carboxylic acids from hydrides Esters from hydrides Hydrides from aldehydes Hydrides from aldehydes Alkyls from aldehydes Ketones from aldehydes Ketones from ketones Alkyls from alkenes (Hydrogenation of Alkenes) Acetylenes from halides; also acetylenes from acetylenes Esters from alcohols; also esters from carboxylic acids Alkyls from alkenes (Conjugate Reduction) Alkyls from alkenes (Conjugate Reduction)
How to Use the Book to Locate Examplesof the Preparationor Protection of MonofunctionalCompounds. Examples of the preparation of one functional group from another are found in the monofunctional index on p. xvii, which lists the corresponding section and page. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of this index. Section 1 gives examples of the reactions of acetylenes that form new acetylenes; Section 16gives reactions of acetylenesthat form carboxylic acids; and Section 31 gives reactions of acetylenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, and transposition are found in Sections 1, 17, 33, and so on, lying close to a diagonal of the index. These sections correspond to such topics as the preparation of acetylenes from acetylenes: carboxylic acids from carbox-
INTRODUCTION
xix
ylic acids; and alcohols, thiols, and phenols from alcohols, thiols, and phenols. Alkylations that involve conjugate additions across a double bond are found in Section 74E (Alkyls, Methylenes, and Aryls from Alkenes). Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Section 199 (Alkenes from Aldehydes) and Section 207 (Alkenes from Ketones). The aldol condensation can be found in the chapters on difunctional compounds in Section 324 (Alcohol, Thiol-Aldehyde) and in Section 330 (Alcohol, Thiol-Ketone). Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and alkenes are also indexed on p. xvii. Sections (designated with an A: 15A, 30A, etc.) with “protecting group” reactions are located at the end of pertinent chapters. Some pairs of functional groups such as alcohol, ester; carboxylic acid, ester; amine, amide; and carboxylic acid, amide can be interconverted by simple reactions. When a member of these groups is the desired product or starting material, the other member should also be consulted in the text. The original literature must be used to determine the generality of reactions, although this is occasionally stated in the citation. This is only done in cases where such generality is stated clearly in the original citation. A reaction given in this book for a primary aliphatic substrate may also be applicable to tertiary or aromatic compounds. This book provides very limited experimental conditions or precautions and the reader is referred to the original literature before attempting a reaction. In n_o tnstanceshouida citation in this book be taken as a completeexperimentalprocedure. Failureto refer to the original literature prior to beginninglaboratory work could be hazardous. The original papers usually yield a further set of references to previous work. Papers that appear after those publications can usually be found by consulting Chemical Abstracts and the Science Citation Index. Classification and Organization of Reactions Forming Difunctional Compounds. This chapter considers all possible difunctional compounds formed from thegroups acetylene, carboxylic acid, alcohol, thiol, aldehyde, amide, amine, ester, ether, epoxide, thioether, halide, ketone, nitrile, and alkene. Reactionsthat form difunctional compounds are classified into sections on the basis of two functional groups in the product that are pertinent to the reaction. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-aminoalcohols, 1,3-aminoalcohols, and 1,4-aminoalcohols are included in a single section (Section 326, AlcoholAmine). Difunctional compounds that have an oxide as the second group are found in the appropriate section (Sections 278-290). The nitroketone product of oxidation of a nitroalcohol is found in Section 386 (KetoneOxide). Conversion of an oxide to another functional group is generally found in the “Miscellaneous” section of the sections concerning mono-
xx
INTRODUCTION
functional compounds. Conversion of a nitroalkane to an amine, for example, is found in Section 105 (Amines from MiscellaneousCompounds). The following examples illustrate applications of this classification system: Difunctional Product
Section Title
RC=C-CSR RCH(0H)COOH RCH=CHOMe RCHFp RCH(Br)CH2F RCH(OAC)CH20H RCH(OH)C02Me RCH=CHCH2C02Me RCH=CHOAc RCH(OMe)CH2S02CH2CH20H RS02CHpCHpOH
Acetylene-Acetylene Carboxylic acid-Alcohol Ether-Alkene Halide-Halide Halide-Halide Alcohol-Ester
Alcohol-Ester Ester-Alkene Ester-Al kene
Alcohol-Ether Alcohol-Oxide
How to Usethe Book to Locate Examplesof the Preparationof Difunctional Compounds. The difunctional index on p. xviii gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol, Thiol-Ester) contains examples of the preparation of hydroxyesters; Section 323 (Alcohol, Thiol-Alcohol, Thiol) contains examples of the preparation of diols. Some preparations of alkene and acetylenic compounds from alkene and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, the transformation RCH=CHBr --* RCH=CHCOOH could be consider as preparing carboxylic acids from halides (Section25,Monofunctional Compounds)or preparing a carboxylic acid-alkene (Section 322,Difunctional Compounds). The choice usually depends on the focus of the particular paper where this reaction was found. In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Likewise, many citations for reactions found in the Aldehyde-X sections, will include examples that can be placed in the Ketone-X section. Again, the choice is dictated by the paper where the reaction was found. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. As an example, the reaction RCI ROH might be used for the preparation of diols from an appropriate dichloro compound. Such methods are difficult to categorize and may be found in either the monofunctional or difunctional sections, depending on the focus of the original paper. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acids, ester; amine, amide; and carboxylic acid, amide --+
INTRODUCTION
xxi
can be interconverted by simple reactions. Compounds of the type RCH(OAc)CH20Ac(ester-ester) would thus be of interest to anyone preparing the diol RCH(OH)CH20H(alcohol-alcohol). Sourcesof Literature Citations. I thought it would be useful for a reader of this Compendium to see the distribution of citations used in this book (i.e., which journals have the most new synthetic methodology). As seen in the accompanying graph, Tetrahedron Letters and Journal of Organic Chemistry account for roughtly two-thirds of all the citations in Volume 8. This book was not edited to favor one category or type of article over another. Certainly, my own personal preferences undoubtedly creep into the selection of methods, but I believe that this compilation is an accurate representation of new synthetic methods that appear in the literature. Therefore, I believe the accompanying graph accurately reflects those journals where new synthetic methodology is located. I should point out that the category “23 other journals” includes: Accts. Chem. Res.; Acta Chem. Scand.; Angew. Chem. Int. Ed. Engi.; Aust. J. Chem.; Bull. Chim. SOC.Belg.; Bull. Chim. SOC.Fr.; Can. J. Chem.; Chem. Ber.; Coll. Czech. Chem. Commun.; Gazz. Chim. Ital.;Heterocycles; Ind. J. Chem.; Isr. J. Chem.; Izv. Akad. #auk. SSSR; J. Chem. SOC.;J. Her. Chem.; J. Indian Chem. SOC.;Liebigs Ann. Chem.; Org. Prep. Proceed Int.; Perkin Trans. I; Recl. Trav. Chim. Pays-Bas; Tetrahedron Asymmetry; and, Zhur. Org. Khim. In addition, six more journals were examined but no references were recorded.
Journal 23 other journals
Tetrahedron
Bull Chem Soc Jpn
Synthesis
JACS '
Synth Commun
JCS, Chem Comm
Chem Lett
SynLett
J . Org. Chem.
Tetr. Lett.'
xxii
INTRODUCTION
Citations
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER
1
PREPARATION
ALKYNES
OF
&&
SECTION 1: ALKYNES FROM ALKYNES M~O&
2. I. Co2(CO)s, BF3wOEt2, CH$& CHC12 \
D
+
3.CAN.MEOH M e 0
/
/
/
\
\ I
/ (85
15)
-a
G r o v e . % ;Miskevich, F.; Smith, C.C.; Corte, J.R.TetrahedronLett., 1990, 31, 6277.
Br
PhCS-H , l o %PdC ,4% CuI
\
CK-Ph
16%PPh3, N E t 3 , MeCN CN reflux De la Rosa, M.A.; Velarde, E.; BuzrnBn, A, Synth. Cotntriun., 1990, 20, 2059.
CN
Br
59%
82%
O-CEC;;
Me3Si-C=C-H1 CuI ,PPh3 Pd(PPh3)4 , piperidine
~
Brandsrna, L.; van den Heuvel, H.G.M.; Verkruijsse, H.D. S y n A Commun., 1990, 20, 1889.
Ph-
'-
1. BuLi ,THF 2. ZIlClZ
3. Plil , Pd(PPh3)4
c
Ph - CE C- Ph
96%
Yoneda. N,; Matsuoka, S.; Miyaura, N.; Fukuhara, T.; Suzuki, A. Bull. Chetn. SOC.Jpn., 1990, 63, 2124.
2
Compendium of Organic Synthetic Methods, Vol8
Section 4
HCS-CHzOH, NEt3 H 2 0 , 20°C
OH 69%
PdC12[PPh2(rn-C6H4S03Na)lz Bumagin, N.A.; Bykov, V.V.;Be1etskayaJ.P. h v . Akad. Nauk. SSSR, 1990, 39, 2665 (Engl., p. 2418).
Okura, K.;Furuune, M.; mra.M,; Nomura, M.Tetrahedron Letf., 1992, 33, 5363.
SECTION 2: ALKYNES FROM ACID DERIVATIVES 0
1. Ph3P=CHC02Et ,NEt3 2. FWP (750°C)
e
Ph-CSC-H
42%
Aitken. R.A; Seth, S. SynLerf, 1990, 211, 212.
SECTION 3: ALKYNES FROM ALCOHOLS AND THIOLS NO ADDITIONAL EXAMPLES
SECTION 4: ALKYNES FROM ALDEHYDES
Me MeO-P0 CHNz
*
BocHNJ-C=C-H
Me0
67%
Hauske.;Dorff, P.; Julin, S.; Martinelli, G.; Bussolari, J. Terruhedron Lett., 1992, 33, 3715.
SECTION 5:
ALKYNES FROM ALKYLS, METHYLENES AND ARYLS NO ADDITIONAL EXAMPLES
SECTION 6:
ALKYNES FROM AMIDES NO ADDITIONAL EXAMPLES
Section 3
Alkynes from Alcohols
SECTION 7:
ALKYNES FROM AMINES
N”’N* Bn
t)
3
Ph
Ph
1. t-BuOK ,DMF
75°C
Ph
4-
2.3eq.t-BuOK * DMF ,75”C
N, H N“ N‘
+
PhNH2
Ph
75% Paventi, M.; Elce, E.; Jackman, R.J.; Ha! A& Telrahedron Lett., 1992, 33, 6405,
SECTION 8:
ALKYNES FROM ESTERS NO ADDITIONAL EXAMPLES
SECTION 9:
ALKYNES FROM ETHERS, EPOXIDES AND THIOETHERS NO ADDITIONAL EXAMPLES
SECTION 10: ALKYNES FROM HALIDES AND SULFONATES LiC=C-n-C&13 THF-DMPU
o&OTf
-20”~ , 15 min
40
n -CgH 57%
Kotsuki. H,; Kadota, I.; %hi, M. Tetrahedron Lett., 1990, 31, 4609.
MCbz
BrT
C0,Me
Bu3Sn-CS-Me ZnCI;! ,CC4, reflux
Me02Cy csC’Me NHCbz
Williams. R.M,; Aldous, D.J.; Aldous, S.C. J. Org. Chem., 1990, 55, 4657.
z E t r H .C i C
v Cu(CN)ZnI
-78°C + 0°C ,30 min
*
86% Knoess, H.P.; Furlong, M.T.;Rozema, M.J.; Knochel. P. J. Org. Chem., 1991, 56, 5974.
4
Compendium of Organic Synthetic Methods, Vol8
Section 12
I
OMe OMe Dchiai, M.; Ito, T.;Masaki, Y.J. Chem. SOC., Chem. Commun.. 1992, 15. SECTION 11: ALKYNES FROM HYDRIDES For examples of the reaction RCKH -+ RC=C-CPCR~,see section 300 (Alkyne-Alkyne).
NO ADDITIONAL EXAMPLES
mo
SECTION 12: ALKYNES FROM KETONES K@ ,18-CrOWn-6 DMF,RT,20h
Sotirious, C.; Lee, W.; S&&,
acozH COZH
56%
R.W. J. Org. Chem., 1990, 55, 2159. 1. NH2OH
Me-CrC--/
Ph
59%
Boivin, J.; Elkaim, L.; Femo, P.G.; U Tetrahedron Lett., 1992, 32, 5321.
SECTION 13: ALKYNES FROM NITRILES NO ADDITIONAL EXAMPLES
SECTION 14: ALKYNES FROM ALKENES NO ADDITIONAL EXAMPLES
5
Alkynes from Miscellaneous
Section 15
SECTION 15: ALKYNES FROM MISCELLANEOUS COMPOUNDS
N - I P h
1. LDA 2. TsN=CHPh
3. t-BuOK. DMF
*
Ph-Cr C-Ph
850C
Katritzkv. A.R,; Gordeev, M.F. J. Chem. SOC., Perkin Trans. I, 1992, 1295.
SECTION 15A: PROTECTION OF ALKYNES NO ADDITIONAL EXAMPLES
70%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 2
PREPARATION OF ACID DERIVATIVES
SECTION 16:
ACID DERIVATIVES FROM ALKYNES CoCl2*6 H2O , KCN , CO 5N KOH ,PhMe ,90°C
Ph- CE C-H
Ni(CN)y4 H20, 1 am PEG - 400
Ph
Ph
- l C O , H
65% Lee, J-T.; Alper. H, Tetrahedron Lett., 1991, 32, 1769.
SECTION 17:
2%
ACID DERIVATIVES FROM ACID DERIVATIVES
Keinan.E.;Sahai, M. J. Org. Chem., 1990, 55, 3922.
Fields.;Behrend, S.J.; Meyerson, S.; Wizenburg, M.L.; Ortega, B.R.; Hall, H.K.Jr. J. Org. Chem., 1990, 55, 5165.
1. DCC , CHzClz 2. CH2=CHS02Ph Ph4C02H
Barton, D.H.R.; Chem, C-Y .;
c
Ph-CO,H
3. mCPBA ,CH2C12 4. TFAA ,22OC57% overall 5 . K2CO3 , MeCN ,22"C Tetrahedron Lett., 1991, 32, 3309.
7
Acids from Alcohols
Section 18
1.
n-Cl lH23-CO2H
>::
,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 ph
cat. Me
Nlslund, J.; Welch. C.J. Tetrahedron Asymmetry, 1991, 2, 1123.
90%
Alcohols from Aldehydes
Section 34B
?CHO OBn
EtzZn, 20 h
23
\/\/\ -
-
57%
OBn OH
20% PhkMe
(78% dr) Soai.;Hatanaka, T.; Yamashita, T. J. Chem. SOC., Chem. Commun., 1992, 927. Soai;Watanabe, M. J. Chem. SOC.,Chem. Commun., 1990, 43. HO'
- N B ~ ~
ZnEt2, PhMe , RT ,?A h
PhCHO
t
PhL
+
+
OH
Et
OH Ph-
Et
(91
2)
91%
(1
99)
80%
NMez
Kimura, K.; Sugiyama, E.; Ishizuka, T.; Kunieda. T, Tetrahedron Lell., 1992, 33, 3147.
Jq
Et2Zn , PhMe , 0°C , 3 h
PhCHO
I-Bu
+
PhqEt OH
l-BU
83%
(93%ee)
also - conjugate addition of Et2Zn Bolm.;Schlingloff, G.; Harms, K. Chem. Ber., 1992, 125, 1191. Bolm.;Ewald, M.; Felder, M. Chem. Ber., 1992, 125, 1205 [conjugate addition]. OH
HO
EgZn , -40°C
PhCHO
OH P&Et
85%C&
(91% e e , S)
78%
- N 2 N J
Mori, A.; Yu,D.;
PhCHO
Bli
SynLett, 1992, 421.
Mea
EtzZn , Ti(OiPr)4,0°C , PhMe c
TosHN
OH
PAEt OH
(81% ee , S)
Ito, K.; Kimura, Y.; Okumura, H.; Katsuki. T, SynLetL 2992, 573.
81%
24
Compendium of Organic Synthetic Methods, Vol8
Section 34B
Heaton, S.B.; Jones. GLB Tetrahedron Lett., 1992, 33, 1693.
NON-ASYMMETRIC ALKYLATIONS
(y
OH
1. Li p,p'-di-1-butylbiphenylide
THF , -78°C
SF%
-
79%
Cohen. T,;Doubleday, M.D.J. Org. Chem., 1990, 55, 4784.
,SbCl3-Fe
-I
PhCHO
2 5 T , 20 h
Wang, W-B.; Shi. L-L; Xu,R-H.; m
0 Ph,TeMe
0 BPh,
-
OH
Ph
.
&
98%
n . Y-Z, J. Chem. SOC., Perkin Trans. I, 1990, 424.
1. BuLi 2.PhCHO 3. 1 h
55%
c
Shl.; Zhou, J.L.; H!une. Y-7.. J. Chem. Soc., Perkin Trans. 1, 1990, 2847. PhCHO , MezFe.3 LiCl THF , -78"C+ RT
I
w
18 h
OH 83%
Also works with Co reagents: Kauffmann.; Laarmann, B.; Menges, D. Tetrahedron Lett., 1990, 31, 507.
SiF3
PhCHO , resorcinol
.
NEt3 CH2Ch1 RT
20h
2%
OH Ph*
Kira.;Sato, K.:Sakum-L J. Am. Chem. Soc., 1990, 112, 257. '
OH
93%
Section 34B
Alcohols from Aldehydes
e- , PhCHO , DMF B u ~ N 1C0 4
&Br
Tokuda.;Uchida, M.; Katoh, Y.;
*
Ph
25
ll"J,
80%
Chem. Lett., 1990, 461.
Bu3SnH, AIBN
L
CHO
&Ph
80%
(1: 1 trans:cis)
Yadav, V.;
Can. J. Chem., 1991, 69, 779. 1. Ba ,THF
OH 97:3
(>99:1 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
73%
34
Compendium of Organic Synthetic Methods, Vol8
Section 39
KI,DMF,RT * t-Bu--(>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 <75%
95%
36
aection 41
Compendium of Organic Synthetic Methods, Vol 8
I
1 '
BuLi , ether, -78°C cthylene oxide, CuCN -65°C -+ 25°C
I Wang, W.; DAndrea, S.V.;Freeman, J.P.; Szmuszkovicz. LJ. Org. Chem., 1991, 56, 2914. 1. n-PrSNaTol , NMP reflux (Dean-Stark) 2. HCI * 96%
GsH
NMP = N-methyl-2-pyrrolidinone
&YI LL&.
J. Org. Chern., 1991, 56, 3728. 1. BqSnH , air
PhMe ,20°C
Ph-Br
2.NaBk.EtOH
* Ph
OH
-k
Ph
80%
14%
Nakamura.; Inubushi, T.; Aoki, S.; Machii, D. J. Am. Chem. Soc., 1991, 113, 8980.
SECTION 41: ALCOHOLS AND THIOLS FROM HYDRIDES
3
OH
OH
90%
TFP= I,l,l-trifluoropropanone Mello, R.; Cassidei, L.; Fiorentino, M.; Fusco, C.; Curci. R. Tetrahedron Lett., 1990. 31, 3067.
0
[RU30(Pfb)6(0Et2)3+ MeCN , air (3 a m ) , 75°C 105 mol. catalyst
pfb = perlluorobutyrate
(5
15 turnovers Davis, S.; I&~QJ& J. Chem. Soc., Chem. Commun., 1990, 250.
1)
Section 41
Alcohols from Hydrides
37
I . Cuo , 0 2 ,Me3N-0 MeCN , 75°C. 6h
H CO2H
2.0.5MHCI
OH
quant.
Reinaud. 0,; Capdevielle, P.; Maurny, M. J. Chem. SOC.,Chem. Commun., 1990, 566.
0~~
CO+' - inontmorillonite
180°C. 2 h Fries rearrangement
96%
rc *-
Ts
4%
Pitchumani; Pandian, A. J. Chem. Soc., Chem. Commun., 1990, 1613.
&
OH
&
;-
(65
9)
26
66%
b a s s , N.; Wang, Q.;O l a h . S y n L e i t , 1991, 39. Rhizopus 28°C. arrkiws I8 h
0
-
0
0 ."&",I
HO& O H +
HO
42%
27%
Ouazzani,J.; Arsenivadis. S , ;Alvmz-Manzaneda, R.; Cabrera, E.; Ouvisson, G . Tetrahedron Lett., 1991, 32, 647.
0
Mucor plumbeus CBS 110-6 2d
a Me
0
+
o&,,,OH
OH
66%
/
22%
Hammoumi, A.; Revial, G.; DAngelo, J.; Girault, J.P.; Azerad, R. Tetrahedron Lett., 1991, 32, 651.
W
Oxone, TBA, 21 h 10 B U ~ N H S O ~ / C H ~ C I ~ aq. acetone , RT (dark) NaHCO3
Kumarathasan, R.; Hunter. N.R, Org. Prep. Proceed. Int., 1991, 23,651.
quant.
38
Compendium of Organic Synthetic Methods, Vo18
a
Section 41
1. HF ; S02CIF 2.90%H202, HF
-10°C -+ 0°C >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$0 OMeOM@Me e o m O M . ]
OH I
Ph
THF , -78°C
84%
(94% ee) J. Chem. SOC., Chem. Commun., 1992, 494. Bu3SnH , TBAF , 0°C
*
0
OMe PhylMe OH
OMe Me
+ phLA -OH
0 ) 81% with BuZSnClH , 0°C (10 90) 72% Shibata. I,; Yoshida, T.; Kawakami, T.; Baba, A.; Matsuda, H. J. Org. Chern., 1992, 574049. (100
Bu
<=orev.,; Link, J.O.Tefrahedron Leu., 1992, 33, 3431.
;'
Cheng, X-M.;Cimprich, K.A.; Sarshar, S. Tetrahedron Lett,, 1991, 32, 6835.
42
Section 42A
Compendium of Organic Synthetic Methods, Vol8
Ph2SiH2, AgBF4, “HF 0°C , 6 h
Ph
OH
Phi\
c
86%
(83% ee , S )
N-. R w - N
Nishivama. H. ; Yamaguchi, S.; Kondo, M.; Itoh, K. J. Org. Chem., 1992, 57. 4306.
NON-ASYMMETRIC REDUCTION
*&
1. LDA ,THF-HMPA Cl-SiMe$I
SiMe3
2. 3. Bu3SnH. MeLiPhH ,THF AIBN 4. H20
w; Kane, R.R.; Obeyesekene, N.U. Tetrahedron Lett., 1990, 31, 1531. THF
quant.
Mittakanti, M.; Peters, J.L.; Morse. K.W, J. Org. Chem., 1990, 55, 4464.
Ph
1
Ph
A1 ,NH3 ,NHdCI, 25°C
)I))))))
-
Ph)’
OH Ph
98%
Sata.;Nagaoka, T.; Goto, T.; Saito, M. Bull. Chem. Soc. Jpn., 1990, 63, 290. NaBH4, MeOH
0
Ph
Rao,;Synth. Commun.. 1990, 20, 45.
HC02NH4, Ni(R), RT
Ph
MeOH , 3 h
+
JO”
0
10) 90%
(90
-
Ph y N H2
91%
Ph
Chen. F-E,; Zhang, H.; Yuan, W.; Zhang, W-W. Synth. Commun., 1991, 21, 107.
43
Alcohols from Ketones
Section 42A
C02Et
PhLi 2. HNTMSz , THF ,,-9OOC TMSI
PhCHO
Tph\**' Bso~co2Et
-78°C Ranu. B.C,; Das, A.R. J. Org. Chem., 1991, 56, 4796.
70%
0'"
0.1% RuC12(PPh3)3
2.4 eq. NaOH , iPlOH * 89% reflux, l h Chowdhury, R.L.; Btickval1. J-E.J. Chem. SOC., Chem. Commun., 1991, 1063. BqSnH , TBAF, THF RT.5h
OH
99%
shibah. I,; Yoshida, T.; Baba, A.; Matsuda, H. Chem. Lett., 1991, 307. NaBH4, CaC12, MeOH
0 Fujii, H.; Oshima.;
0
.
(97 Chem. Lett., 1991, 1847.
+
(ItoH 3)
92%
Fisher, G.B.; Harrison, J.; Fuller, J.C.; Goralski, C.T.; Sincaram. B. Tetrahedron Lett.. 1992, 22, 4533. REVIEWS:
"Bakers Yeast as a Reagent in Organic Synthesis" Servi. S . Synthesis, 1990, 1. "Practical and Useful Methods for the Enantioselective Reduction of Unsymmetrical Ketones" Singh. V.K, Synthesis, 1992, 605.
SECTION 42B: ALKYLATION OF KETONES, FORMING ALCOHOLS Aldol reactions are listed in Section 330 (Ketone-Alcohol)
44
Compendium of Organic Synthetic Methods, V o l 8
MeLa(OTfl2, THF -78"C.lOmin =
P h L P h
Section 42B
Me OH Ph&Ph
98% Collins. S,; Hong, Y.; Hoover, G.J.; Veit, J.R. J. Org. Chem., 1990, 55, 3565. BuLi , Yb(OTfl3
-
THF , -78OC
Me
c
(99
1)
91%
Molander.; Burkhardt, E.R.; Weining, P. J. Org. Chem., 1990, 55, 4990.
c1
[Li biphenylide , Cd2]
0-0
,TIIF
83%
-78°C + -35°C J. Org. Chem., 1990, 55, 5045.
Wu, T-C.; Xiong, H.;
1 . 2 SmCpz , THF
OH
OH
-3OOC
C l e \ v Me-
2. cyclohexanone
4)
(1
Collin, J.; Bied, C.;
BnO-CHO
57%
Tetrahedron Lett., 1991, 32, 629. $:
~
3
ether, -78°C
3
_____c
CuLi-PBu3
SiMe,
:
92%
( > 2 0 1)
Burke. S.D.; Piscopio, A.D.; Marron, B.E.; Matulenko, M.A.; Pan,G. Tetrahedron Leu., 1992, 32, 857. 2 SmI2, THF , c2 h cat. Fe@BM),
Me Me
-78°C
I
+ RT
* Me 3
DBM = dibenzoyl methide
Molander.;McKie, J.A. J.
Org. Chem., 1991, 56, 4112.
Me
e 88%
Section 44
45
Alcohols from Alkenes
1.
6Fe(C0)zCp BF3 , ether
c
2. NaI ,wet acetone
77%
Jiang, S.; TUQLL Tetrahedron Lett., 1991. 32, 4619. BuCeCIz
( y E H
77%
ultrasound used with CeC13-7 H 2 0 to prepare cerium reagent m v e s . N.;Lyford, L. Tetrahedron Lett., 1992, 33,4759.
SECTION 43: ALCOHOLS AND THIOLS FROM NITRILES 300°C. iPrOH
-CN
-OH
+
73%
hydrous zirconium oxide Takahashi, K.; Shibagaki, M.; Matsushita, H. Chem. Lett., 1990, 311.
SECTION 44: ALCOHOLS AND THIOLS FROM ALKENES Ph
+
Me
.-I300 0 0
1. [(+)-BINAPJRhCI PhMe,-5"C,72h 2. NaOH ,H2O2
Ph H,&oH M~ 73% (38%ee,S)
Sato, M.; Miyaura, N.; Suzuki. A, Tetrahedron Left., 1990, 31, 231.
PhKato, K.;
\
Co(acac)L, 0 2
iPrOH
c
OH Ph
Ph-+ 17%
46%
Ph
2 8%
Yamada.; Takai, T.; Inoki, S.; Isayama, S. Bull. Chem. Soc., Jpn., 1990, 63, 179. Ru~(CO)IZ, 180°C ( C - C ~ H I I )H~z ~0 HCOzMe , 10 h 'shaking' autoclave=
Jenner. G.Tetrahedron Lett., 1991, 32, 505.
0 9%
+
( T O H 60%
Compendium of Organic Synthetic Methods, Vol 8
46
Section 44
1.9-BBN 2. NaoOH
OSiMe,,t-Bu H0
HO with tbexylborane
HO
(1 3
1
-)
93%
(1
15
1)
91%
Harada.;Matsuda, Y.; Wada, I.; Uchimura, J. J. Chem. SOC.,Chem. Commun., 1990, 21. [RhH(PEt3)3] , 120°C ,EtOH
-OH
L
94% (n:iso = 2.22) D.L J. Chem. SOC.,Chem. Commun.. 1990, 165.
MacDougall, J.K.; -ikon.
fi
hv (Vycor) , H202 MeCN,15h
*
66% 34% Sonawane.;Bellur, N.S.; Shah, V.G. J. Chem. Soc., Chem. Commun., 1990, 1603. 1.
a". d
H
L i B b , THF 2. H 2 0 2 , NaOH
94%
OH
+
-OH 6%
w; Nunokawa, Y.; Masuda, Y.; Hoshi, M. J. Chem. SOC.,Chem. Commun., 1991, 205. 4
ph
NaBH4, iPrOH ,100"C CH2C12 , co (500 psi)
Q
Pph3 , 2 2 h
@Rh (COD)
"-( (95
p
h
b
H
5)
83%
OH
Zhou, J-Q.; Alper. H. J. Chem. Soc., Chem. Commun., 199Z, 233.
(>99
-a.
A&;
1)
15%
Xu,Z.; Morken, J.P.; Houri, A.F. J. Am. Chem. SOC.,1991, 113, 8950.
Section 44
Alcohols from Alkenes
47
1. 0.01% [PdCl(l~-C3H5)12
HSiCl3 ,0.02% R-MOP
-
2. KF , KHC03 , H202
R-MOP = (R)-2-methoxy-2-diphenylphosphino-1.1'-binaphthyl Uozumi, Y.; Lee,S-Y.; Jlavashi. T. Tetrahedron Lett., 1992, 33,7185.
2% Rh(PPh3)CI , THF *
2. NaOH , aq. H202 EtOH , THF
H
O
W
(99
+ ? OH 1)
Evans. D.A,; Fu, G.C.; Hoveyda, A.H. J. Am. Chem Soc., 1992, 114, 6671. 1. (J":B-H
Harrison, K.N.;Ma&$. 1.
%Ph
-
,250c
R o
CnLaCH(SiMe& 2. H202, NaOH T.J.J. Am. Chem. Soc., 1992, 114, 9220.
0
:B-
, PPh3
*
2% RhCI(PPh&
2. H 2 0 2 , NaOH
OH
Ph
, J
O -H 78%
+
P h X O H
(199 1) Burgess.; van der Donk, W.A.; Westcott, S.A.; Marder.; Baker, R.T.; Calabrese, J.C. J. Am. Chem. Soc., 1992, 114, 9350. 5% LiBEt3H, THF, 5 h 20°C , (Bu0)zBH
(95
5)
OH
12%
Arase. A,; Nunokawa, Y.; Masuda, Y.; Hoshi, M. .I Chem. . Soc., Chem. Commun., 1992, 51
SECTION 45:
ALCOHOLS AND THIOLS FROM MISCELLANEOUS COMPOUNDS NO ADDITIONAL EXAMPLES
48
Compendium of Organic Synthetic Methods, Vol8
Section 45A
SECTION 45A: PROTECTION OF ALCOHOLS AND THIOLS AgB
. PhH
87%
w 0 O BH r H 2 C O NO2
* w 0 O NO,
Z ( 1 0 F/mol) , aq. r-BuOH , TFA
Fukase, K.; Hata, N.; Oishi, T.;
TetrahedronLett., 1990, 31, 381.
0
0
Me 1 . 3 eq. Me3SiOTf, 5 min CHzClz , 0°C 2. neutral A1203 (grade I)
N3 Bou, V.; Vilarrasa, J. Terrahedron Lett., 1990, 31, 567.
t-BuPh20
NaH , HMPA
H 0’”
0°C. 5 min
OSiMe,t-Bu
OSiMeg-Bu
80% Shekhani.;Khan, K.M.; Mahmood, K.; Shah, P.M.; Malik, S. TetrahedronLett., 1990, 31, 1669.
0,0,
SiMeZPh
Cl,,O,,
NEt3
&>OM% KBr ,AcOH
* &nhMe
SiMe2Ph 91%
OBn
92%
Boons, G.J.P.H.;Elie, C.J.J.; van der Marel, G.A.; van Boom, J.H. TefrahedronLett., 1990, 31, 2197. 1. TfOSiOMezt-Bu CHzClz ~
2. Me$
Kim.;Kee, I S . Tetrahedron Lett., 1990, 31, 2899.
n-C8H17
OSiMe,t-Bu 95%
Section 45A
Protection of Alcohols
49
I
93%
in dioxane, Bn cleaved but not OSiR3 Tosbima, K.; Yanagawa. K.; Mukaiyama, S.; BnOH DEAD , PPh3
H
O
>Bnoh Tetrahedron Lett., 2990, 31, 6697.
h
o o
o o
74%
Baiwa. JS,; Anderson, R.C. Tetrahedron Lett., 1990, 31, 6973. FeCI, ,MeCN , RT
n-C 1OH2 1OTMS
-
1 min
n -C1OH2 1 0 H
other Lewis acids were also used
C o r t . S y n r h . Commun., 1990, 20. 757.
1. (MeO)$H2 ,pTsOH CH2C12, 10 h
n-C& 170H 2. PhSH ,pTsOH * n-C8H170- SPh
CH2C12,7 h Dieter. R.K,; Dam, R. Org. Prep. Proceed. Int., 1990, 22, 63.
56%
hv ,NBS ,CaCO3 aq. CC14
OMe
86%
OMe
ev. R . K ; Hehemann, D.G. J. Org. Chem., 1990. 55, 378. DMAP , NEt3
t-BuMe2Si0
OHOH
OHOH
Naif. V.; Buenger, G.S. Org. Prep. Proceed. Int., 1990, 22, 3. 1.0.9 MezSn(SMe)z BF3*OEt2,O0C, 16 h
Ph-
OTHP 2. H 3 0 +
)r
Ph-OH
Sato, T.; Otera.; Nozaki, H. J. Org. Chem., 1990, 55, 4770.
90%
Compendium of Organic Synthetic Methods, Vo18
50
(PPh3)4RhH, TFA
Section 45A
17
&c8H b
EtOH ,reflux
HO
98%
m; Brown, E.G.; Sobolov, S.B. .I. Org. Chem.. 1990, 55, 3691. EtsSiH, CH2C12 1% Rhztpfih , 2 h
Y OH
* -
OSiEt,
pfb = perfluorobutyrate
88% ;High, K.G.; Bagheri, V.; Pieters, R.J.; Lewis, P.J.; Pearson, M.M. J. Org. Chem., 1990, 55, 6082.
OTHP
bentonite earth (TONSIL) acetone, RT , 3 0 min
Me
Me
Cruz-Almanza. R.; Pkrez-Flores, F.J.; Avila. M. Synrh. Cotntnun., 1990, 20, 1125.
0
-
Oh- CF3 0
ether, 2OoC, 30 min
c
Keumi. T,; Shimada, M.; Morita, T.; Kitajima, €1. Bull. Chern. SOC..lpn., 1990, 63, 2252.
HoLo HO
HO
1. BuzSnO , PhMe reflux , 4 h
2. Pd(PPh3)4, THF RT, 1h OAc OAc
HO
HO
2)
(8
89%
Holzanfel. C.W.; Huyser, J.J.; van der Merwe, T.L.; van Heerden. F.R, Heferocycles,1991, 32, 1445.
3 eq. MgBr2, ether, RT 2.5 eq. BUSH
~z-C~H~~OMOM
t
~z-C~H~~O 97% H
Kim. &; Kee, I.S.; Park, Y.H.; Park, J.H. SynLRil, 1991, 183.
Section 45A
Protection of Alcohols
OSiMe2t-Bu
51
q~
OSiMe2t-Bu
KF-A1203, MeCN
RT
78%
OSiMe2t-Bu
ultrasound used in cases when deprotection is slow Schmittling, E.A.;
Tetrahedron Lett., 1991, 32, 7207. dihydropyran ,CH2C12 sulfonatedcharcoal MS3A.Sh
O H -
-OTHP 97%
Synth. Commun., 1991, 21, 2329.
htmyJ&
N3 ,NaH ,DMF
Br*
Ph-
*
*
O-OH
Ph-0-O
1. H2, Pd-C
92%
3. DDQ ,- 5 0 ~ Fukase. K.; Hashida, M.; Kusumoto. S , Tetrahedron Lett., 1991. 32, 3557.
4
NHBoc
MPMol OH BrBa(0H)yOBu , DMF ~ M o ~ Q + N H B n r 32 h
58%
DDQ
Fukase, K.; Yoshimura, T.; Hashida, M.; Kusumoto. S. Tetrahedron Lett., 1991,32, 4019.
OSiMepBu aq. NEt3, H2SiF6, 1 h MeCN
TIPSO
P
TIPSO
O 75%
H
+
P
O
OH
17%
Pilcher, A S . ; Hill, D.K.; Shimshock, S.J.; Waltermire, R.E.; DeShone. P.J. Org. Chem., 1992, 57, 2492.
0°"
Ph3CC1, DBU
Colin--;
0"'82
Girard, J-P.; Ross, J-C. Tetrahedron Lett., 1992, 33, 2689.
H
Compendium of Organic Synthetic Methods, Vo18
52
Section 45A
1. SiF4(gas), MeCN
~,,,OSiMej-Bu t-Bu
23"C, 20 min
i
t-Bu
2. H20
m e v . E J.; Yi, K.Y. Tetrahedron Lett., 1992, 33, 2289.
Yoshida. J.; Ishichi, Y.; Nishiwaki, K.; Shiozawa, S.; boe. S, Tetrahedron Letr., 1992. 33, 2599. BHpTHF, 20°C. 24 h
Cossv. JJ Bellosta, V.; Muller, M.C. Tetrahedron Left., 1992, 33, 5045. TiC13-Li-THF, reflux 14 h
* n-Cl6H33-OH
~-CI~H,~-O-CH~P~
Kadam, S.M.; Nayak, S.K.; Banerii.A.Tefrahedron Lett., 1992, 33, 5129.
85%
-
AIC13 PhNMe2
Ph-oBn
anisole, CH2C12
=-
Ph-OH
93%
Akivama.; Hirofuji, H.; QzakiLi Bull. Chem. S O ~Jpn., . 1992, 65, 1932. dihydropyran ,CH2CI2
Ph-
OH
H2SO4 , silica gel 10 min ChBvez.; Godinez, R. Synth. Commun., 1992, 22, 159.
Ph-OTHP
96%
AI(PO4)3 , dihydropyran
reflux , 15 min = Q,WP 97% G~&LL&J.M.;Garcia, A.; Lafont, F.; Luna, D.; Marinas, J.M. Synth. Commun., 1992, 22, 2335.
Section 45A
Protection of Alcohols
-
53
Zandbergen, P.; Willems, H.M.G.; van der Marel, G.A.; Brussee. J. ; van der Gen, A. Synth. Commun., 1992, 22, 2781. L a c & , dihydropyran H2C12,RT,4h
OH
OTHP
Bhuma, V.; IGmam&L Synth. Commun., 1992, 22, 2941.
OMe
3 eq. TMSCl , RT 1.5 eq. anisole
Ph-O
Ph A OH
90%
30 min
Akivama.;Shima, H.; Qzaki. S, SynLetf, 1992,415.
0
7;,acetone
2.5%
20°C ,45 h
BnO
90%
&
= HO
MXI~&AB.A.; Muxworthy, J.P.; Baggaley, K.H. SynLett, 1992, 646.
69%
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 4 PREPARATION OF ALDEHYDES
SECTION 46: ALDEHYDES FROM ALKYNES NO ADDITIONAL EXAMPLES
SECTION 47: ALDEHYDES FROM ACID DERIVATIVES 6.5% (Cy3P)2RhCHC12 PhH/NEt3, H2,SO"C w
1abn.65h Grushin, V.V.;
65%
J. Org. Chem., 1991, 56, 5159.
n-CgHzlCOOH
1.2 eq. Pv 2. LiAlH&Et2)3
3. H 3 0 +
*
n-CgH21-CHO
90%
Cha.,Lee, J.C.; Lee, H.S.; Lee. S.E. Org. Prep. Proceed. &., 1992, 24, 327. '
PhCHo Yu, H.K.B.; S&m#zJ
1. Bu3SnLi 2. Me3SiCN
3 . 3 eq. BuLi 4 . 0 3 ,CH2C12
>
PhCOOH
63%
Tetrahedron Lett., 1992, 33, 6787, 6791.
SECTION 48: ALDEHYDES FROM ALCOHOLS AND THIOLS
diglyme , 120OC 12 h
Kulkami.;Mathew, T.S. TetrahedronLett., 1990, 31, 4497.
55
Aldehydes from Alcohols
Section 48
0
also with 2" alcohols to give ketones Campestrini, S.; DiFmiaJ,; Modena.fi, Bortolini, 0. J. Org. Chem., 2990, 55, 3658.
'electrolytic' MnO2 hexane , RT , 13 h
-OH
*
-CHo 78% Tsuboi. S.; Ishii, N.; Sakai, T.; Tari. I,; Utaka, M. Bull. Chem. SOC. Jpn, 1990, 63, 1888. Cr03 - "wet alumina"
-
PhCH2OH
PhCHO
90%
also for the preparation of aryl kelone from aryl alcohols Hirano, M.; Kuroda, H.;
Bull. Chem. SOC. Jpn., 1990, 63, 2433. NBS , AIBN , CC4
PhCH20SiMe3
9 5 0 8~min ~
m
PhCHO
87%
Mark6 I.E.; Mekhalfia, A.; Ollis. W.D, SynLett, 1990, 345. Me3NHCI-CrO3 ,MS 4A
-OH
CH2C12,20 h Acharva. S . P,; Rane, R.A. Synthesis, 1990, 127.
-OH
c
e- ,Pt electrodes ,pH 6.8 Ru(Upy )(~PY)OI'~
e C H O
n
C
H
75 95
O 41%
trpy = 2,2'.6',2"-terpyridine
Navarro, M.; Pe Giovani. W.F.; Romero. J.R, Synrh. Commun., 2990, 20, 399.
(13: 1 retention:isomerization) Xiao, X.;
Synth. Commun., 1990, 20, 3125.
Compendium of Organic Synthetic Methods, Vol8
56
PhCH,OH
Akamanchi.:Iyer, L.G.;
Section 48
CH2C12, RT ,30 min
PhCHo
94%
Meenakshi, R. Synth. Commun., 1991. 21, 419. hydrous zirconium oxide benzophenone, xylene
* PhCHO 81% Enux Kuno. H,; Shibagaki, M.; Takahashi, K.; Matsushita, 11. Bull. Chem. SOC. Jpn., 1991, 64, 312. PhCH2OH
RuC13 , CC4, aq. NaOCl
c-
O -H
-CHO
65°C 90% Ogibin, Yu.N.; Ilovaiskii, A.I.; Nikishin, G.I. Izv. Akud. Nauk. SSSR,1991, 40, 115 (Engl., p.99).
-
PhI . Pd(OAch Bu~NCI',D I 6 Ph
-OH
CHO 82%
Lefferv. T,Tetrahedron Lea., 1991, 32, 2121. e (3.5 F/mol) , Pt electrodes 5% Na2CO3-25% NaBr , 0°C
Go*
* n-CgH,g,CHO
PhC02
'CH2C12 H20
89%
oxidation of 1" alcohols much faster than 2" alcohols Inokuchi, T.; Matsumoto, S.; Torii. S. J. Org. Chem., 1991, 56,2416. Inokuchi, T.; Matsumoto, S.; Fukushima, M.; Toni. S,Bull. Chem. SOC. Jpn. 1991, 64, 796. Inokuchi, T.; Matsumoto, S.; Nishiyama, T.; J. Org. Chem., 1990, 55, 462. Inokuchi, T.; Matsumoto, S.; Nisiyama, T.; Torii. S . SynLeft, 1990, 57. 1. [C13C0]20, DMSO CH2C12, -78°C
(iPr),SiQ. H Me
OH
2. mt3 , -78°C -+ 20°C
(iPr)$iQ H MeXc~o
84% Palomo. C.; Cossio, F.P.; Ontoria, J.M.; Odriozola, J.M. J. Org. Chem, 2991, 56, 5948.
Section 48
Ma, Z.; Bobbitt.
Aldehydes from Alcohols
57
J.M.J. Org. Chem., 199Z, 56, 6x10. , RT , overnight
Ph+OH
c
RuTMP(0)z
p h f i CHO
81%
TMP = tetramethylpyrazole
Higuchi, T.; Ohtake, H.; Hirobe. M. Tetrahedron Lett., 1991, 32, 7435. 1. DMSO , -78°C triphosgene
-OH
c
2. NEt3 , -78°C -+ RT
-CHO
82% Rivero, I.A.; Somanathan.;Hellberg, L.H. Org. Prep. Proceed. Int, 1992, 24, 363.
2 CuBr2 , 2 LiBr , 13 h
Ph
OSnBu3 Bu3SnOt-Bu Yamaguchi, J.; E&&J, Chem. Len., 1992, 423. CrO3, DMSO, RT.4 h
-OH
ph&CHo
78%
-CHO
68%
Lou, W-X.; Lou. J-D, Synth. Commun., 1992, 22, 767.
n-C,H,,CH,OH
'I'PCD , DMF , 80°C lh
*
n-C,Hl,CHO
80%
TPCD = tetrakis-pyridino-cobaltdichromate = [Py4Co(HCrQ)21 Hu. Y,; Hu, H. Synch. Commun., 1992, 22, 1491. SeOz , SiOz, RT
H
OH
-
r-BuOOH , CHzC12 15 h
O H C Y 7 - O H
Kalsi, P.S.; Chhabra. B.R. ; Singh,. J.; Vig, R. SynLett, 1992, 425.
90%
58
Compendium of Organic Synhetic Methods, Vol8
Section 50
REVIEWS:
"Oxidation of Alcohols by Activated DMSO and Related Reactions: An Updale: Edwell. 'CIC Synthesis, 1990, 857.
SECTION 49: ALDEHYDES FROM ALDEHYDES Conjugate reductions and Michael Alkylations of conjugated aldehydes are listed in Section 74 (Alkyls from Alkenes). ISiC13 , RT ,20 min w
OEt
PhCHO
958
Elmorsv.;Bhatt, M.V.; Pelter, A. Tetrahedron Lett,, 1992, 33, 1657. OAc
CAN, Si02 CH2CI2
c
OMe
OMe
Cotelle.; Catteau, J-P. Tetrahedron Lett., 1992, 33, 3855. Related Methods:
SECTION 50:
Aldehydes from Ketones (Section 57) Ketones from Ketones (Section 177) Also via: Alkenyl aldehydes (Section 341)
ALDEHYDES FROM ALKYLS, METHYLENES AND ARYLS
Manmez.;Alvarez, R.M.;
Barcina, J.O.; de la Moya Cerero, S.; Vilar, E.T.; Fraile, A.G.; Hanack, M.; Subramanian, L.R. J. Chem. Soc., Chem. Commun., 1990, 1571.
also, EtPh converted to acetophenone Chem. Lett., 1990, 1445.
Imamoto.;Koide, Y.;
Section 52
59
Aldehydes from Amines
DCA-MV” ,FeC12 hv (visible light) ,
Me
02*3h
DCA = 9,10-dicyanoanthracene; M V + =~ methyl viologen ketones are fromed form ACH2R a t a m a r i d ; Jroundi, R. Tetrahedron Lerr., 1991, 32, 4291.
SECTION 51: ALDEHYDES FROM AMIDES LiAIH(NEt& , THF +
RT
-CHO
59%
Cha.;Lee, J.C.; Lee, H.S.; Lee, S.E.; Kim, J.M.; Kwon, 0.0.;Min, S.J. Tetrahedron Lerr., 1991, 32, 6903.
SECTION 52: ALDEHYDES FROM AMINES
Ph
[2 Cu(N03)z/Hz02/2 HzOl
LNH,
.L
Ph-CHO
aq. MeCN Capdevielle, P.; Maumy, M. Tetrahedron Lert., 1990, 31, 3891. hv , cat. I2 ,air NMe2 ‘
Gangloff, A.R.; Judge, T.M.;
Ph,N-
95%EtOH
*
60%
-CHO
n-C6H13
66% J. Org. Chem., 1990, 5.5, 3619.
1. BuLi , THF 2. BnCl 3. H30’
* Ph-CHO
85%
Shah, J.H. J. Org. Chem., 1991, 56, 2955.
PhCH=N-OH
bakers yeast
*
PhCHO
68% (with ultrasound 96%) Kamal. A,; Rao, M.V.; Meshram, H.M. J. Chem. SOC.,Perkin Trans. I, 1991, 2056.
60
Compendium of Organic Synthetic Methods, Vol 8
1. [TiC14, NaI , MeCN] MeCN ,20 min 2. aq. NaOH
Section 53
3
*
63%
H
n-C7H15
Balicki. R,; Kaczmarek, L. Synth. Commun., 1991. 21, 1777.
PhCH2NH2
1. PhS02CI 2. KO2 ,-TIIF, 24 h
park. K.H,; Lee, J.B.Synth. Commun.,
PhCHO
e
%%
1992, 22, 1061.
Ketones from Amines (Section 172)
Related Methods:
SECTION 53: ALDEHYDES FROM ESTERS 1. & e O k
-
Pd(PPh3)4, THF RT,45h
PPh2
Ph Me-CHO
v
2. aq. HCI
80% (48% ee)
Hiroi. K,; Abe, J. Tetrahedron Lett., 1990, 31, 3623. Et3SiH, Pd-C acetone
t
D o d H
Me0
94%
Furuvama.;Lin, S-C.; Li, L. J. Ani. Chem. SOC.,1990, 112, 7050. n-C3H7C02Et
1. Li(EtZN)$ilH THF , -78°C
Cha.;Min, S.J.; Lee, H.S. Org. Prep. Proceed.
0
Ph
A SPh
n-C3H7.CHO
. t
2. H30'
82% lnf., 1992, 24, 335.
1 . Li , THF, -78°C 2. MeOH
-
PhCHO
Penn.; Owens, W.H. Terruhedron Lert., 1992, 33, 3737.
98%
Section 54
Aldehydes from Ethers
s-;.
SECTION 54:
61
ALDEHYDES FROM ETHERS, EPOXIDES AND THIOETHERS
Ph3Si
2 eq.MABR , PhMe
*
r-Bu 1-Bu
88%
(1: 100 erythro:threo)
MABR = B r c ) 0 , $ 0 3 r r-Bu Me
eCH
Ph3Si0
f-311
Maruoka, K.; Sato, J.; Yamamoto.J.Am. Chem. Soc., 1991, 113. 5449.
MABR , CH&l,, -2OT SbFS , PhMe , -78°C
loo)
(0 (83
17)
99%
47%
MABR = methyl aluminum bis-(4-bromo-2,6-di-t-butylphenoxide) Maruoka, K.;Bureau, R.; Ooi, T.; Yamamoto. H. SynLett, 1991, 491. OBn 1.
=dSiMe3
TMSOTf , MeCN
OMe
0°C , 3 0 h 2 . 0 3 , CHzClz
B;:oqoBn 24 h
BnO
CHO
10%NEt3 Bno=oBn BnO iPrOWCH2C12 BnO
CHO
-78°C
49% (10:l
@a)
Kobertz, W.R.; Bertozzi, C.R.; Bednarski. M.D, Tetrahedron Lett., 1992, 33, 737.
(77% ee)
Malacria.;Cilloir, F. Tetrahedron Left., Z992, 33. 3859. Related Methods:
SECTION 55:
Ketones from Ethers and Epoxides (Section 174)
ALDEHYDES FROM HALIDES AND SULFONATES e- , Fe(CO)5 ,MeCN
-Br
Et4NBr
-
-CHO
Yoshida.; Kobayashi, M.;Amano, S. J. Chem. Soc., Perkin Trans. I, 1992, 1127.
71%
Compendium of Organic Synthetic Methods, Vol8
62
CO (80 am), Bu3SnH
Br
Ph&
*
Section 56
ph/\/CHo
AIBN , PhH ,80°C 65% Kusano, K.;Ogawa, A.; Kambe, N.; Sonoda.N.. Am. Chem. SOC., 1990, 112, 1295. ByLLL;Kusano, K.; Masumi, N.; Yamazaki,H.; Ogawa, A.; Tetrahedron Lett., 1990, 31, 6887.
m;
1.
n-C,H 17-1
MeO-@eNa
POT EFrther
n-C8HI7CH2CHO
*
77%
2. NBS , H 2 0 Ynevama. K,; Kitagawa, K. Tetrahedron Lett., 1991, 32, 3385. TPCD , DMF , 100°C
PhCH2Cl
U
t
PhCHO
lh TPCD = tetrakis-pyridino-cobaltdichromate = [Py4Co(HCrO&l ; Hu, H. Synth. Commun., 1992, 22, 1491.
54%
SECTION 56: ALDEHYDES FROM HYDRIDES
0
iPrONO . HCI
0
w
Me-
Gordeeva, G.N.; Kalashnikov, S.M.; Gordeev, A.N.; Popov, Yu.N.; Kruglov, E.A.; Imashev, U.B. Zhur. Org. Khim.,1990, 26, 2199 (Engl., p. 1896). HF-SbFS , CO (20 a m )
*
O
H
C
~
C
NH2 DMSO - HCI , CuCI2
Br
Ir
OHC
Liedholm. B,J. Chem. SOC., Perkin Trans. I, 1992, 2235,
O
81%
(93:7 4,4':2,4') Tanaka, M.; Souma, Y. J. Chetn. Soc.. Chem. Cotnmun., 1991, 1551.
0:
H
aNH2 98%
Br
Section 59
63
Aldehydes from Alkenes
0 Boese, W.T.;
ocHo
hv (A. = 366 nm) CO (1200 psi)
91%
Q
Tetrahedron Letf., 1992, 33, 2119.
SbF5-HS03F1CO 168 min
+
CHO
1
CHO
(76
24) 90%
CHO
2%
Souma, Y.J. Org. Chem, 1992, 57, 2671.
Tanaka.;Iyoda, J.;
SECTION 57: ALDEHYDES FROM KETONES
,/.,
PhMe2Si
OBn
O.lM,launH2 PdC , RT , EtOH
20 h
80%
0
0 Cirillo, P.F.; Panek. J.S. Tetrahedron Lert., 1991, 32, 451. SECTION 58: ALDEHYDES FROM NITRILES 1. Li(hexylzN)3AIH
PhCN
THF , 0°C
2. H 3 0 +
c
Ph-CHO
u; Lee, S.E.; Lee, H.S. Org. Prep. Proceed. Int., 1992, 24, 331.
“f,””
99%
SECTION 59: ALDEHYDES FROM ALKENES
0 L O
Steckhan.
e‘ , H20 2% (Bu4N)s(HzO)RuSiW ,1039
EL: Kandzia, C. SynLerr, 1992, 139.
Related Methods:
c
0QCHO L O
Ketones from Alkenes (Section 179)
68%
64
Compendium of Organic Synthetic Methods, Vol8
SECTION 60:
Section 60A
ALDEHYDES FROM MISCELLANEOUS COMPOUNDS
-
YO NMO , DMSO , N v C l n-C9H19€H0 n-C9H19 50% 0 Nikolaides, N.; Godfrey, A.G.; QmmJ. Tetrahedron Lett., 1990, 31,6009.
n-C 1lH23
1. Sn(SPh), , EtOH
--
n-CliH23- CHO
2. SnC12-2 H20,3 h L-tartaric acid ,40"C NaHCO3, NaHSO3 3.2M HCI Urpi, F.; Vilarrasa, J. Tetrahedron Lett., 1990, 31, 7499. LN02
81%
1. BuLi ,THF , -78°C 2. n-C5HllI, 4 eq. HMPA b n-C5HllCH0 t-BuOSO2Ph -78°C - RT 83% 3. LiBr , K2CO3 ,48h H2O/ether, reflux Chemla, F.; lulia.;Uguen, D.; Zhang, D. SynLett, 1991, 501. Julia.;Uguen, D.; Zhang. D. SynLett, 1991. 503.
SECTION 60A: PROTECTION OF ALDEHYDES ethanedithiol ,Lac13 CH2C12, RT , 4 h
-CHO
Garlaschelli, L.; Vidari.G.Tetrahedron Lett., 1990, 31, 5815.
Liao, Y.;
-
; Zhu, F-H. J, Chem. SOC., Chem Commun., 1990, 493.
PhCHO , R T , 3 0 min
Me
66%
NrC
=
Lee, S-B.; Takata, T.; Endo. T, Chem. Lett., 1990, 2019.
Mey--Ph
quant.
Section 60A
65
Protection of Aldehydes
Amberlyst 15, acetone/HCHO H 2 0 , 80°C, 15 h
*
80%
a 2
U l i n i . R.; P e t h i , M. Synthesis, 1990, 336.
A C H O
PhCHo
ethane dithiol ,hexane
H-Y zeolite, reflux 90% l h Kumar. P,; Reddy, R.S.; Singh, A.P.; Pandey, B. Tetrahedron Lett., 1992, 33, 825.
DDQ , MeCN ,H 2 0 , RT
w
PhioMe OMe
Tanemura.;Suzuki, T.; Horaguchi, T. J.
PhCHO
75%
Chem. Soc., Chem. Commun., 1992, 979.
HM-zeolite , H20, PhMe
P h q oOEt Et
reflux, 9 h
Ic
PhCHO
89%
Rao. M.N.; Kumar, P.; Singh, A.P.; Reddy, R.S. Synth. Commun., 1992, 22, 1299.
wCHO
HOCH2CH20H, PhH catalyst, reflux, 30 min quant.
Otera J,; Dan-oh, N.; Nozaki, H. Tetrahedron, 1992, 48, 1449.
Compendium of Organic Synthetic Methods, Volume 8 Edited by Michael B. Smith Copyright 0 1995 by John Wiley & Sons, Inc.
CHAPTER 5 PREPARATION OF ALKYLS, METHYLENES AND ARYLS This chapter lists the conversion of functional groups into methyl, ethyl, propyl, etc. as well as methylene (CH2), phenyl, etc.
SECTION 61: ALKYLS, METHYLENES AND ARYLS FROM ALKYNES (iPr)3SiO- C i C (CH2h /-7BU
0
N2
Me0
W E , hv
OMe
-
OSi(iPrI3
54%
Danheiser.;Cha, D.D. TetrahedronLett., 1990, 31, 1527. 1.5 eq. KOH ,37”C
DMSO , EtOH , 2 4 h 58%
Toshima, K.;Ohm, K.;Ohtake, T.;
OMe Tetrahedron Lett., 1992, 32, 391.
Ph
Bdwa. A; Austin, D.J.; Chiacchio, U.; Kassir, J.M.;Rescifina, A.; Xu,S.L. Tetrahedron Lett., 1991, 32, 5923.
-hi. E,; Harring, L.S.; Owczarczyk, 2.;Mohamud. M.M.; Ay, M. Tetrahedron Lett., 1992, 33, 3253.
Section 62
AIkyls from Acids
67
(R = TMS:R = OH = 5.2)
Bao, J.; Draagisich, V.; Wenglowsky, S.; y u l f f . W.D. J. Am. Chem. SOC., 1991, 113, 9873.
.
C02Me
1. SmIz-THF Pd(PPh314
, -78°C + 0°C
OH
57%
OH C02Me
2. =/
Inanaea.,Sugimoto, Y.;Hanamoto, I. Tetrahedron Lett., 1992, 33. 7035.
&
Me02C 210°C. 24 h
72%
Grissam.;Calkins, T.L. Tefrahedron Left.,1992, 33, 2315.
SECTION 62:
ALKYLS, METHYLENES AND ARYLS FROM ACID DERIVATIVES SiMe, 0 0 mesitylene , 165°C nitrobenzene, 125°C
+o
0 72% 0%
Kraffi.;Rich.; McDemott, P.J. J. Org. Chem., 1990, 55, 5430.
21% 100%
Compendium of Organic Synthetic Methods, Vol8
68
SECTION 63:
Section 63
ALKYLS, METHYLENES AND ARYLS FROM ALCOHOLS AND THIOLS SiMq
6
*
BF3oOEt2, CHzClz -78°C + RT
Schmitt, A.: &issin. H IJ, SynLett, 1990, 40.
Me
p
95%
(98:2 trans:cis)
1. N B S , hv ,ccl4 2. BuzCuLi , ether
OH
3. TMSI ,MeCN , heat
Me 74%
&mkiA& Tetrahedron Lett., 1991, 32, 3411. BR3, TfOH
*
Ph-CH20H
+
Ph-CH2-R
Ph-CH3
R = Me 57% R = Et 11% R = iPr 0.1% Mah.;Wu,A.; Farooq, 0.J. Org. Chem., 1991, 56, 2759.
43% 89% 99%
Nation-H , PhH
+OH
95"C'1hb
81%
Yamamoto. T.; Hideshima, C.; Surya Prakash, G.K.; Olah, G.A. J. Org. Chern., 1991, 56, 2089.
c.j$'F s n-C1 3H27
F
PhMe,Smin 2. Bu3SnH, PhMe 5 min Barton, D.H.R.; Blundell, P.; Dorchak, J.; Jang. D.O.; 47, 8969.
OH
*
13H27
CH3
95% Tetrahedron, 1991,
Section 65
Alkyls from Alkyls
69
OMe 1.5.7 eq. SnC4
-78°C + 25°C
2. ph-
OH
Me
,1h
77%
Me
Anele. S.R,; Amaiz, D.O. J. Org. Chem., 1992, 57, 5937.
SECTION 64:
ALKYLS, METHYLENES AND ARYLS FROM ALDEHYDES
*& acHo
1. NbCIs ,Zn ,DMWPhH
n-CSH 1 1 - (3C- n-C,H
11
n - w11
2. 2.6-lutidine 25"C, 10h
/
3.
CHO
/
93%
n-C#
11
25OC ,30 min Kataoka, Y.; Miyai, J.; Tezuka, M.; Takai.; Oshima, K.; Tetrahedron Lett., 1990, 31. 369.
MeMgl, NiC12(dppe)
c
Ph
Ph
93%
Tzeng, Y-L.; Yang, P-F.; Mei, N-W.; Yuan, T-M.; Yu, C-C.; h h . T-Y. J. Org. Chem., 1991, 56, 5289. REVIEWS:
"Chiral Acetals in Asymmetric Synthesis"
Alexakis.;Mangeney, P. Tetrahedron Asymmetry,
1990, I , 471.
Related Methods: Alkyls, Methylenes and Aryls from Ketones (Section 72)
SECTION 65:
ALKYLS, METHYLENES AND ARYLS FROM ALKYLS, METHYLENES AND ARYLS 1. BuLi , THF , -78°C
*
3. BuLi , THF , -78°C 84% 4. Et-I Rabideau. P.W,; Dhar, R.K.;Clawson, D.K.; Zhan, 2. Tetrahedron Letf., 1991, 32, 3969.
70
Compendium of Organic Synthetic Methods, Vol8
0 N
1. NaH 2. NMP , ZnCl2, RT 3. PdC12(PPh3)2 , PhBr
H
b
RT , PPh3,2 h 4. 140°C, 2 h
p
p
h +
Section 48
Oph+ Ph-Ph
N
H
H
40%
50%
10% .. . . m ; Gusmerol, M.; Riva, R. Tetrahedron Left., 1992, 33, 1755.
2.4 eq. Fe(C104)3 "FA, CH2C.12, RT
Me0
0
Me0
Me0
Me0
0
Tanaka, M.; Mitsuhashi, H.;
74%
Tetrahedron Left.,1992, 33, 4161.
SECTION 66: ALKYLS, METHYLENES AND ARYLS FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 67: ALKYLS, METHYLENES AND ARYLS FROM AMINES 1.2.2 eq. Li naphthalenide THF , -78°C 2. Me2S04 Kawase, T.; Fujino, S.; Oda.M. TetrahedronLeft.,1990, 31, 545.
60%
SECTION 68: ALKYLS, METHYLENES AND ARYLS FROM ESTERS NaBPh4, THF Pd(dba)z , PPh3
80% 60°C Legros, J-Y.; Fiaud, J-C. Teirahedron Lett., 1990, 31, 7453.
71
Alkyls from Esters
Section 68
PhSnMe3, 5% Pd(dba)2
Ph-oAc
Ph
Ph-
Dh4F , LiCl ,23"C 69 h
57%
DeI Valle, L.; Stille. J.K.;b d u s . L S , J. Org. Chem., 1990, 55, 3019. X eq. LifLClOo
PhSe
OAc
2 min addition of BuMgBr
* P h S e B u i-
X = 2; 2 = 2 min X = 5 ; 2 = 40rnin
75% 13%
Btickvall. J-EL;Sellkn, M.; Grant, B. J. Am. Chem. Soc., 1990, 112, 6615.
0 II
tC02Me
NaWBuLi , O°C
CO,Me
2. CA(OAC)T€I~O, reflux
-
3. 2N HC1
BU
phs&
25% 87%
OH I
WMe C02Me
17%
-chi. M,; Hasebe, K.; Higashi, H.; Uchida, M.; Irie, A.; Minami, T. J. Org. Chem., 1990, 55, 1611.
heat
H
H
0
via benzyne cycloaddition-retroDick- Alder
0
43%
Meirk, D.P.; Guitih, E.; Castedo. L. Tetrahedron Lett., 1990, 31, 143.
-
cat. Pd(dba)2 , PhZnCl
J-L p
60%
Ph
Ph
Ph 0
(9.4%ee)
Fiaud, J-C.; Legros, J-Y. Tetrahedron Lett., 1991, 32, 5089. (PhMqSi)*Cu(CN)LiZ
L O ' P h ;.I-
333 1.
THF -ether
* L S i M e 2 P h 83% Higgins, D.; Lawrence, N.J.; Thomas, A.P. J. Chem. Soc., Perkin Trans. I, 1992,
72
Compendium of Organic Synthetic Methods, Vol8
pSiM
TMSCHzMgCl 5% Ni(acac)2, ether*
@ y e 2 Ph
Ph
Sengupta, S.; Leite, M.; Raslan, D.S.; Quesnelle, C.;
SECTION 69:
Section 69
J. Org. Chem., 1992, 57, 4066.
ALKYLS, METHYLENES AND ARYLS FROM ETHERS, EPOXIDES AND THIOETHERS
The conversion ROR + R R ( R = alkyl, aryl) is included in this section.
Me0
-
BuCu*BF3
i Me
0
0 0 N
BU
4Me
65%
0
Ludwig, C.; Wistrand, L-G. Acta Chem. S c a d . , 1990, 44, 707.
h,fe
2. Me1 , O°C
Me ;-
I.K,mF 4h
*Meo+
Me OMe 72%
Denurra, T.; Melloni, G.; Piroddi, A.M. J. Org. Chem., 1990, 55, 5386.
K 0
N*H
BuCu(CN)Li. LiCl
BF3,THF
Ishibuchi, S.; Ikematsu, Y.;Ishizuka. T.;
Et02C
co+k
fi
K 0
N-H
%
Tetrahedron Lett., 1991, 32, 3523.
BujSnH, AIBN
N-N l
PhSe
0
+
Ph
Kim.; Kee, IS.; Lee, S. J. Am. Chem. Soc., 1991, 113, 9882. Me0,C”
N
OMe
kO,Me
SiMe,
TiCl4, CH2Cl2 -78T
* Me@C
‘“h k02Me
(73:27 cktrans)
Shono. T.; Fujita, T.; Matsumura, Y. Chem. Lett., 1991, 81.
80%
Alkyls from Halides
Section 70
SECTION 70:
73
ALKYLS, METHYLENES AND ARYLS FROM HALIDES AND SULFONATES
The replacement of halogen by alkyl or aryl groups is included in this section. For the conversion of Rx + RH (X = halogen) see Section 160 (Hydrides from Halides and Sulfonates).
Bz'
AIC13, 10°C
C02H -
Bz'
91% 9% Kronenthal. D.R,; Mueller, R.H.; Kuester, P.L.; Kissick, T.P.; Johnson, E.J. Tetrahedron Lett., 1990, 31, 1241. BuzCuMgBr, -40°C THFlerher , I h
\IC0,Et
C0,Et
t
OTf
Bu
53% Petit, Y.; Sanner, C.; LarchevEque, M. Tetrahedron Lett., 1990, 31, 2149.
OMe
PhB(OH)2, Pd(PPh3)4 DMF , aq. Na2CO3
OMe
OTf Fu, J-M.;
Ph
Tetrahedron Lett., 1990, 31, 166.5.
Sph
c1
BuCu(CN)ZnI TIIF, 18 h -78°C -+ 25°C
Chen, H.G.; Gage, J.L.; Barrett, S.D.;
'fSph
88%
Bu (21/79 WZ)
Tetrahedron Lett., 1990, 31, 1829.
1. Z ~ u s c DMF
CO2t-BU 80%
also undergoes conjugate addition reactions Majid, T.N.; Knochel. P, Tetrahedron Lett., 1990, 31, 4413.
Compendium of Organic Synthetic Methods, Vol8
74
0
1. Pd(PPh3)d , NaOH THF , reflux, 6 h
Ph
*
2. NaOH ,H202
Section 70
Ph
Soderouist.;Santiago, B. Tetrahedron Lett.. 1990, 31, 5541. Soderouist.;Santiago, B.; Rivera, I. Tetrahedron Lett., 1990, 31, 4981.
WOT~ 0
OH
Bu4Sn DMF, ,3PdC12(PPh3)2 q.Licl 95°C. 2.5 h
74%
0 OH 0 OH Tamayo, N.; Echavarren.;Paredes, M.C.; Farifla, F.; Noheda, P. Tetrahedron Lett., 1990, 31. 5189.
n -
@fB.O
c1
)
1. BuLi , THF, -78°C 2. PhMe ,reflux, 36 h
3. H+ , AcOH
* Bu-
55%
Brown. H.C,; Rangaishenvi, M.V. Tetrahedron Lett., 1990, 31, 7113, 7115. Bu3SnH, AIBN PhH , 80°C
OMOM
OMOM
OMOM
(80
64%
20)
Nagai, M.; Lazor, J.; Wilcox. C .S, J. Org. Chem., 1990, SS, 3440.
PhBr
10%NiBr2(PPh3)2, Zn , THF 10% EtdI
-
Ph-Ph
99%
luoda.;Otsuka, H.; Salo, K.; Nisato, N.; Oda, M. Bull. Chem. SOC.Jpn., 1990, 63, 80. 1. SnzMe, LiCl , THF
Pd(PPh34 ,reflux 2. PhBr , iPrzNEt , PhMe
OTf
cat. 2,6-di-t-butyl-4-
4
methylphenol Pd(PPh3)d. reflux
Ph
(9 1
Stork. G,; Isaacs, R.C.A. J. Am. Chem. SOC., 1990, 112, 7399.
+&Ph 9)
58%
Section 70
Alkyls from Halides
M
Zncl Arcadi, A.; Burini, A,;
e
O
75
V OTf
Pd(PPhd4, THF
/
OMe
41%
u; Delmastro, M.; Marinclli, F.; Pieuoni, 8 . SynLen, 1990, 47.
Br
-
Takahashi, S.; Jvfori. N, J. Cheni. SOC., Perkin Trans. I, 1991, 2029.
Br
Li[Bu4In] , R T , 3 h
+
Bu
80%
Araki, S.; Shimizu, T.; Jin, S-J.; Butsugan...I.Chem. SOC.,Chew Cornmun., 1991, 824. PhMgBr , ether, 20 h 10% NiClz(dppf) reflux * o Yuan, K.; Scott. WJ, Tetrahedron Lett., 1991, 31, 189.
c , h
77%
1)
(2.59
Burke. S.D,; Piscopio, AD.; Kort, M.E. Tetrahedron Let(., 1991, 32, 855. Br
1. B u q n L i , THF 2. aq. AcOH
n-CsH17-( Br
n-C8H17-/
Bu
77%
Harada. T.; Kotani, Y.; Katsuhira, T.; Oku. A. Terrahedron Lett., 1991, 32, 1573
Ph,C-CI
PhzTIBr, PhLi , ether
t
Ph3C-Ph
Mark6 LE,; Kantam, M.L. Tetrahedron Lett., 1991, 32, 2255. Mark6. ISEL;Southern, J.M.; Kantam, M.L.SynLerr, 1991, 235.
74%
89%
Compendium of Organic Synthetic Methods, Vol8
76
Section 70
Mitchell. M.B.; Wallbank, P.J.TetrahedronLett., 1991, 32, 2273. 1. BuLi, t-BuOK
"[-
A S i M e 3
=Hi;,"
'
A \
SiMe3
* Bu
Bu
(3.3 Li, L-H.;
SiMe3
+
:
1)
95%
Wane., Chan, T.H. TetrahedronLett., 1991, 32, 2879.
83% Yamato. T,;Sakaue, N.; Suehiro, K.; T ~ s ~ K M.o Org. , Prep. Proceed. h t . , 1991, 23, 617.
PhH , AICl3 , 6 h
80°C
t
* (9 97% ee ( S ) Piccolo. 0,;Azzena IL; Melloni, G.; Delogu, G.; Valoti, E. J. Org. Chem., 1991, 56, 183.
0
1. (FS02)20 , EtN(iPr)2,2 h
CH2C12, -78T
OH
2. PhZnCl , THF , LiCl 5% Pd(PPh3)4 , 50°C
90%
m a ;Fuller, C.E. J. Org. Chem.. 1991, 56, 3493. P
h
w C1
BuTi(OiPr), ,THF ,-70°C 7.5% Cub2 LiCl , 6 h
Ph
Arai, M.:IUauuJ. J. Org. Chem, 1991,56, 5490.
PhICI2
b
BuLi , THF , -80°C
-
>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
<'OZH
H 2 , EtOH
2% Me
p.
NBD = norbornadiene
Rh(NBD)Cl
quant.
(96% ee)
go
Chiba, T.; Mivashita. k;Nohira, H.; Takaya, H. Tetrahedron Lett., 1991, 32, 4145.
OAc
k& , P t 0 2 , EtOAc NEt,. RT, 2 d
OAc
OAc
Katsuki, J.;
JmmgaATetrahedron Lett., 1991, 32, 4963.
88%
Ph3SnH, BEt3 , PhH 25T,6h
Nozaki, K.; Oshima. K.; Utimoto, K, Bull. Chem. Soc. Jpn., 1991, 64, 2585.
Compendium of Orgaiiic Synthetic Methods, Vol8
94
bakers yeast, 64 h
%rMe
n-C,H, I
Section 74D
Me n-C5H1+fMe
*
0
24%
0
(>99%ee) Sakai.;Matsumolo, S.; Hidaka, S.; Imajo, N.; Tsuboi, S.; Bulf. Chem. SOC. Jpn., 1991, 64, 3473. SmI2, AcNMez ,THF
Ph
Me
-
Ph&C02Et
EtOH , 12 h
co2,,
96%
Inanaea.;Sakai, S.; Hmda, Y.; Yamaguchi, M.; Yokoyama, Y. Chem. Lett.. Z991, 2117. “ZEt
Zn , AcOH , 2 h
C02Et
98%
”)))
Marchand.; Reddy, G.M. Synthesis,
COZEt
1991, 198,
Pd(OAC),, HC02K DMF ,60°C
94%
Arcadi, A.; Bernocchi, E.; Cacchi.;Marinelli, F. SynLett, 1991. 27,
C02Me Cabrera, A.;
1. SmI2, THF 2. HMPA , RT , 3 0 min
*
&C02Me
67%
Tetrahedron Lett., 1992, 33, 5007.
4 am H2, MeOH ,25”C 24 h
’
* qumt.
Ph OMe
Me0
Me
(40% ee) Me
Sjenet.;Pinel, C.; Mallart, S.; Juge, S.; Cailhil, N.; Laffitte, J.A. Tetrahedron Lett., 1992,
33, 5343.
Section 74E
Conjugate Alkylation of Alkenes
95
(52%ee , R) Saburi.;Ohnuki, M.; Ogawawara, M.; Takahashi, T.; Uchida, Y. Tetrahedron Lett., 1992, 33, 5783.
Q
&
COzEt =/ ,DBU,DMEU
185°C.24 h
CO2Et
*
DMEU = 1,3-dimethyl-2-imidazolidinone
80%
Hwu.; Kakimelahi, G.H.; Chou, C-T. Tetrahedrontett., 1992, 33, 6469. SECTION 74E: Conjugate Alkylations
n-Bu Ph
Met
0
>-.
B(OiPr)2 0.1 q.BFpOEt2, PhMe
Ph 0 78% Hara, S.; Hyuga, S.; Aoyama, M.; Sato, M.; Suzuki. A. Tetrahedronktf.;1990, 31, 247. 2. 1. MezCu(CWi2 (PhMezSi)Cu(CN)Liz
4
m
3.aq.NH4CI 60%
Me
+
M?e
SiMe2Ph
M~
SiMe2Ph
major Lett., 1990, 31, 311.
Lee, S.-H.; -Tetrahedron
0
THF/&er/ptane
(CN)Li,
CO ,-1 10°C 4min
73% (12:l trans:cis)
; Elworthy, T.R. Tetrahedron Lett., 1990, 31, 477.
96
Section 74E
Compendium of Organic Synthetic Methods, Vol8
OTs EtZCuLi , THF
* &OH
-78°C 3 RT , 135 min
80%
Et
Charonnat.;Mitchell, A.L.; Keogh, B.P. TelrahedronLeli., 1990, 31, 315.
Eid, C.N. Jr.;
'
TetrahedronLett., 1990, 31, 305.
e- , (HglSCE electrodes) dimethyl d o n a t e n-BudNBr, MeCN
Me Me
Me
(89%) Sowell, C.G.; Wolin, R.L.; Little. R.D. TetrahedronLett., 1990, 31, 485.
Bno-w
ether, -78°C , 3 0 min 0
Me
0
+
2. NaOMe ,MeOH 14h , 2 5 T no yield
,!w?.M.E.; Lew, W. Tetrahedron Lett., 1990, 31, 623.
1.5 MeMgBr , [Cu] ether:THF , 1 h
%e
0
60
CO,E~ 3.0 TMSCl , -46°C
OBn
0
40
A
Sakata, H.; Aoki, Y.; Buwa iima. I, Tetrahedron Lett., 1990, 31, 1161.
0
C02Et 99%
Section 74E
97
Conjugate Alkylations of Alkenes
8
MesSnCu-SMez ,THF Li(Bu3SnCuSPh) -78°C
*
6 0
85%
SnBu3 I U Lesheski, E L.E.;. Kiely, ; J.S. Tetrahedron Lett., 1990. 31, 1837. 0
1.LDA9THF,-78"C
2. EtZAICl , -40°C
c
u
JSMe 3. Kpegba, K.; bieknaJ Tetrahedron Lett., 1990, 31, 1853.
s quant.
SMe
+ Me
b,..
MezAgMgBr THF CH~CIZ,
MesRh,THF
Me
/
61% Kauffmann, T,; Hiilsdiinker, A.; Menges, D.; Nienaber, H.; Rethmeier, L.; Robber, S.; Scherler, D.; Schrickel, J.; Wingbermiihle, D. Tetrahedron Lett., 1990, 31, 1553.
f i
SnBu3
I. MeLi 2.0.5CuCN-LiCI
also reacts with halides, epoxides, etc.
L1Dshutz.;Ung, C.; Elworthy, T.R.; Reuter, D.C. TetrahedronLett., 1990, 31, 4539. 4 eq. EgSiH , sealed tube r-BuOOt-Bu, 140°C PhH
Me3Si also cyclization with unconjugated dienes Kraus. G.A,; Vivas, S. TetrahedronLett., 1990, 31, 5265.
98
Section 74E
Compendium of Organic Synthetic Methods, Vo18
rl
benzophenone ,PhH hv (>300 nm) , 1 2 mM
n
S
20 min 57% Nishida. A,; Nishinda, M.; Yonemitsu, 0. Tetrahedron Lett., 1990, 31, 7035.
*
C02Me
CHCl3,
@0
NEt,
e- (1.8 F/mol) ,DMF EhNBr , Pt cathode
t
Y C O , M e cc1, 78%
Sbono,;Ishifune, M.; Ishige, 0.; Uyama, H.; Kashimura, S . Tetrahedron Lett., 1990, 31, 7181.
Lipshutz, B.H,; Sharma, S.; Reuter, D.C. Tetrahedron Lett., 1990, 31, 7253.
I
1 CpZZrClz, DCE ,PhMe , 0"
0
2. CuCN , B u C K L i THF 0 3. -23°C 0 Ireland. R.E; Wipf, P. J. Org. Chem., 1990, 55, 1425.
COzBHA I. BULi, THF
2. LiBEl3H ,THF 3.Me1,HMPA
4.N a B h , MeOH 5. 10% aq. HCl
* 75%
BHA = 2,6-di-t-butyl-4-(methoxyphenyl)-l -naphthalenecarboxaldehyde
Tornioka.;Shindo, M.; Koga, K. J. Org. Chem., 1990, 55, 2276. Tomioka.;Shindo, M.; Koga, A. Tetrahedron Lett., 1990, 31, 1739.
Section 74E
Conjugate Alkylations of Alkenes
*
C0,Et
BuMgBr , MnClz LiCl , THF , 0°C + 20°C CuCl , Me3SiC1
99
y C O , E t Bu 97%
Cahiez.;Alami, M. Tetrahedron Lett., 1990, 31, 7423, 7425.
8
4
PhCH( R)Cu(CN)ZnCl
THF
R - n-C3H7
n-C3H7
SPh
78%
Achyutha Rao, S.; Tucker, C.E.; UuzhdLTetrahedron Lett., 1990, 31, 7575.
Kim, &; Lee, J.M. Tetrahedron Lett., 1990, 31, 7627.
& : L 0
Bu3SnH. AlBN PhH (0.04 M)
SePh
Middleton, D.S.;
[C02Me
65%
; Terrett, N.K. Tetrahedron, 1990, 46, 545.
hv ,DMSO , 4 eq. iPrHgCl
C02Me
4 eq. KI
Russell.;Kim, B.H. SynLett, 2990, 87.
Li I , THF, Cu*Me$iCI 30min
Q% ,
82%
87%
LiDshutz. B.H ; Ellsworth, E.L.; Dimock, S.H.; Smith, R.A.J. J. Am. Chem. Soc., 1990, 112, 4404.
Compendium of Organic Synthetic Methods, Vol8
100
Section 74E
LiAIH4 - S b Q , THF 0°C
0
0 Savama.;Inamura, Y. Bull. Chem. SOC. Jpn., 1991. 64, 306. -SnMq
.
hv
MeCN , 15 h
&
84%
51%
m u w a . A,; Nishigaichi, Y.; Iwamoto, H. Chern. Lerr., 1991, 1013.
Dupuy, C.; Petrier, C.; Sarandeses. L.A.;
Synth. Commun., 1991, 21, 643.
1. SmI2, THF , DMPU
+
I Curran.;Wolin, R.L. SynLetf, 1991, 317.
H- CE C- C02Me
60%
20%
iPr-I, BujSnSnBuj
hv (sunlamp), 85OC 30 min
(1:2.4
C02Me 70%
E:Z)
Curran.;Kim, D. Tetrahedron, 1991, 47,6171.
!&ra&QE
Kim, D.; Ziegler, C. Tefrahedron, 1991, 47, 6189.
[
cat. CpzZrCl2, CH2C12,0°C HCSCH2CH20H CuCN-2 LiCl , THF-ether
(2.8:l trans:cis) U s h u t z . B.H.; Dimock, S.H. J. Org. Chem., 1992, 56, 5761.
82%
Section 74E
Conjugate Alkylations of Alkenes
101
Ph*OMOM SiMq
68%
CsF , DMF
OMOM
Ph
Linderman. R.J.; Ghannam, A.; Badejo, I. J. Org. Chem., 1991, 56, 5213.
0
+%
1. CpzZr(H)CI ,THF RT ,20 min, )))))I 2
.
~
0
3. CuBr=SMez,RT , 1 h wiof.;SmiU'ovich, J.H. J. Org. Chem., 1991, 56, 6494.
CO2Et
A
CI(CF2)411Zn , EtOH bromo(Py) cobaloxime (111)
+
Et02C
. ,
20"C, 1 h
(CF,),CI
Bu. C-M.; Qiu, Y-I>. Tetrahedron Letr., 1991, 32, 4001. 0
B uzCu(CN)Li2 THF , -78°C
n-C6H13T
O M e 90% Bu
Soderauist.;Rosado, I. Tetrahedron Lett., 1991, 32,4451.
Q
+oSiMezr-Bu ,ether OMe
2.5 M LiC104 , 1.2 h
70%
-
6
OSiMe,t-Bu 95%
C02Me
u; Cooke. R.J.; Henry, K.J.; Vander Roest, J.M.Tetrahedron Left., 1991, 32, 4665. TBAF
____c
Mefl:C)Xt
Me yamarnot0.y.;Okano, H.; Yamada, J. Tetrahedron Left., 1991, 32, 4749.
(7:3 dr)
61%
102
Compendium of Organic Synthetic Methods, Vol8
1. MezCu(CN)Li*, -78°C 3h n
2.
Me3Sn
uo
SnMe3 3. MezCu(CN)Liz
*
Section 74E
% 0
0
(91% E,E)
;-
Lee, J.I. Terrahedron Lett., 1991, 32, 7211.
C02t-Bu 1 . BuLi ,THF ,-78°C 2. H3O+
CO2t-BU b
88%
6
(translcis = 3.0)
Cmk,M.P. L J . Org. Chem., 1992, 57, 1495. 1 . MeLi 2. aq. H2SO4
OH
0
Alons0.F.; XusJd. Tetrahedron, 1992, 48, 2709. BhSn
Et3SiC1, -78°C
70%
OSiEt,
Cu(CN)Li
\-I
Me
* 96%
P; Emonds, M.V.M.; Stengel, P.1; OHveira, A.R.M.; Simonelli, F.; Ferreira, J.T.B. Tetrahedron Lett., 1992, 33, 49.
(91:9 trans:cis)
Toru.;Watanabe, Y.; Tsusaka, M.; Gautam, R.K.; Tazawa, K.; Bakouetila, M.; Yoneda, T.; Ueno, Y. Tetrahedron Len., 1992, 33, 4037.
Conjugate Alkylations of Alkenes
Section 74E
103
Me3ToaMeLi ,ether -40°C. 1 h
Me Mark6. I.E.; R e b i h , R. Tetrahedron Lett., 1992, 33, 1763. 1 . 4 eq. Sm12, THF , HMPA 2. CuI*P(OEt)3 , -78°C + -20°C
Ph-
I
3.
#o
Tottleben, M.J.; Curran, P.P.; WiDf. P.J. Org. Chem., 1992, 57, 1740. 1. BnNH2, cyclohexane reflux c
Me-
0
Me
C02Me 2. NaBH3CN, MeOH
Bn >6:1
Dumas, F.; dAngelo, J. Tetrahedron Lett., 1992, 33, 2005.
$
:B.(ZnlCu[CIV]C=CHBu
0'
&C02Me N E:Z)
,MqSiCI
-78°C -+ 25°C , 12 h
n-C,H 1 1 0
Waas, J.R.; Sidduri, A.R.;
57%
76%
Tetrahedron Lett., 1992, 33, 3711. C%CO,, MeCN
Me02C
COzMe add yn-one by syringe pump
Meo2cQc$Me
(88:12 cktrans)
Girard, S.; -Can.
Ph-
J. Chem., 1992, 70, 1265.
Te-
Ph
1. BuzCu(CN)Liz, THF RT 2. -78°C , * 0
0
UPh 77%
Tucci, F.C.; Chieffi, A.; Comasselo.J.V.Tetrahedron Letf., 1992, 33, 5721.
Compendium of Organic Synthetic Methods, Vol8
104
Section 74E
(67
33)
48%
WU. M-L; Wu, C-C.; Lee, P-C. Tetrahedron Lett., 1992, 33, 2547.
1. CUCN,-78°C + -4°C
2,
0
0
mdall.J.K;; Ayers, T.A. Tetrahedron Lett., 1992, 33, 5311. 2 eq. BnMgCl ,CuI TMSCl , TMEDA
Et0,C-
+ E t O , C y ph THF , -78°C + -40°C
73% 24 h van Heerden, P.S.; B e z u m L . . B.C.B.; Steenkamp,J.A.; Ferreira D, Tetrahedron Lett., 1992, 33, 2383.
t-Bu
Dieter.;Alexander, C.W. TetrahedronLett., 1992, 33, 5693. 1. BrCC13 , hv 2. MeOH ,H20
%Me3
3. BuCu(CN)Li , -78°C
0
*
"'9 c1 SiMe3
Cunico.;Zhang, C. Tetrahedron Lert., 1992, 33, 6751.
64%
BnCu(CN)ZnI c
c1
c1
67%
Ph
Ph
Sidduri, A.R.; Budries, N.; k n e a .;IhxhdL Tetrahedron Lett., 1992, 33, 7515.
105
Conjugate Alkylations of Alkenes
Section 74E
Cl(CF2)8I
d C O z E t , Zn , THF cat. SmC13 ,reflux
*
CI(CF&CH,CH,CO,Et 76%
w Zhao, ; G.; Huang,W. Tetrahedron Lett., 1992, 33, 81 19.
Q
PhBr , Ni(bipy)3(BF3)2 DMF ,ZnBr2, Bu4NBr e‘ (Zn anode, C cathode)
+
6,
52%
Sibille, S.; Ratovelomanana, V.; Perichon, J. J. Chem. SOC.,Chem. Commun., 1992, 283.
I
‘OzMe,
.
=tOzMe NHAc
0
EtOH RT ,)))))))I*
-
Sarandeses, L.A.; MouriAo, A.; 4eq.
Zn ,C ~ I
C02Me
”I”y”” 14%
J. Chem. SOC., Chem. Commun.. 1992, 798.
0,BF3*OEtz 0
25°C ,40h
Q--& C02Me
+
NHAc
quant.
Cativiela. C,; L6pez, M.P.; Mayoral, J.A. SynLett, 1992, 121.
0
BuzCuLi , ether
C3cL SiPh3
w
B
u
q SiPh3
0
-78°C
89%
DedInnocenti. A,; Stucchi, E.; Capperucci. A.; Mordini, A.; Reginato, G.; Ricci. A, SynLett, 1992, 329, 332.
ASYMMETRIC CONJUGATE ADDITION REACTIONS
8
DMS , LiCu(n-Bu)R
R=
[ €1Y % N ~
92%(8l%ee,S)
Rossiter.;Eguchi, M. Tetrahedron Lett., 1990, 31, 965.
106
Section 74E
Compendium of Organic Synthetic Methods, Volt?
ABu
[BuLVCuBr] ,ether
*
NH2 M e
63%
(68% de, R)
Me
Dieter. R.K,;Lagu, B.;Deo, N.; Dieter, J.W. Tetrahedron Lett., 2990, 31,4105.
* 0
Ph
catalyst =
ZnEt2, catalyst
ph
b
1% Ni(acac)t
0
Ph
JLb 55% (72% ee, R)
3 m OH
Ph
Hob'
Balm.; Ewald, M . TefrahedronLett., 2990, 31, 5011.
(94 Fang, C.; Suemune, H.; W a i . K,Tetrahedron Lett., 2990, 31, 4751.
6
iPrMgBr , 1% ZnCl2 , THF -9O"C, Me
f
&
Jansen, J.F.G.A.; Feringa, B.L. .I. Org. Chem.. 2990, 55, 4168.
H
fi."-OMe
+ 2.ZnBr2, THF 3. Me2CuLi , -78°C + 0°C
Tamura.;Watabe, K.;
61%
91%
(18% ee)
OH
1. MeCN 25°C
6)
Katayama, H.; Suzuki, H.; -to.
kMe
84%, S Y.J. Org. Chem., 1990, 55, 408.
Section 74E
Ph
107
Conjugate Alkylations of Alkenes
qCPh3 - P hEt n0f C P h 3 0 Et2Zn
Mewph
0
25%
OH
81%
(80%ee, 1S2R)
Soai.;Okudo, M.; Okamoto, M. Tetrahedron Lett., 1991, 32, 95. 1. Me(S-MAPP)CuLi , ether
-78"C,1 h
2.4N NH4CI
bMe 57%
(58% ee , S) Rossiter. B.E.; Eguchi, M.; Hernsndez, A.E.; Vickers, D.; Medich, J.; Marr, J.; Heinis, D. Tetrahedron Lett., 1991, 32, 3973.
$gMe $?:
Rawson, D.J.; M e v e r s . T e t r a h e d r o n Lett., 1991, 32, 2095. BuzCuLi TMSCl
c
0
0
85%
Mevers.~.~.; Leonard, W.R. Jr.; Romine, J.L. Tetrahedron Lett., 1991, 32, 597. 1. BuMgBr , TMSCl cat. CuBreSM9
HMPA , -3OT
2. KF
*
c : p o Bu (93
Sonoda, S.; Houchigai, H.; Asaoka, M.;
+
Bu= 7)
Tetrahedron Lett., 1992, 33, 3145.
81%
108
Section 74F
Compendium of Organic Synthetic Methods, Vo18
c1-,
Ph-@KPh 0 Kanai, M.: Koga, K.; M
Boc
PPh2
,MezCuLi
Me 0
79%
(84%ee , S)
a . K, Tetrahedron Lett., 1992, 33, 7193. EtZZn, Ni(acac)2
Ph
Ph
*
ether, -20°C. 1 h
Et.N
*
Ho
Ph (70% ee , R)
Ph- S a 0
Bolm.;Felder, M.; Miiller, J. SynLett,
0
Et
71%
1992, 439.
REVIEWS:
"The Evolution of Higher Order Cuprates" I&XWLULSynLerf, 1990, 119. "New Aspects of Organmopper Reagents: 1,2- and 1,2- Chiral Induction and Reaction Mechanism" Ibuka, T.; Yamamoto, Y. SynLeff, 1992, 769.
SECTION 74F:
Cyclopropanations, including Halocyclopropanations
Me3SiOHOC &
t
C02Me C02Me
02Me /
t
(dba)3PdyCHC13 PPh3 , THF , reflux
HH
COzMe
C02Me 64%
Trost. B.M,; Urabe, H. Tetrahedron Lett., 1990, 31, 615.
COZEt
Me-
n-C3H7MgBr, CuI
Et02C (6040
E:Z)
Kasatkin. A,N,; Kulak, A.N.; Biktimirov, R.Kh.; Tolstikov, G.A. Tetrahedron Lett., 1990, 31, 4915.
Cyclopropanations of Alkenes
Section 74F
P h d
N
109
0
2d 0-I-menthyl
t
Cu salen derivative catalyst
A-
Ph
+
i=02-l-menthyl
Ph C02-1-menthyl
72% 96% ee 14)
(86
98%ee
dPh ,CH2C12
L-L CO,Me
0
ko
CHN,
b
Tetrahedron Left., 1990, 31, 6005.
Lowenthal, R.E.; Abiko, A.;
cat.
p, y
.Rh-I ' RhI
trans (48% ee, 1S,2S)
h0
Ph
69% (67:33
cis (85%ee , lS,2R)
tramcis)
I)ovle., Brandes, B.D.; Kazala, A.P.; Pieters, R.J.; Jarstfer, M.B.; Watkins, L.M.; Eagle, C.T. Tetrahedron Lett., 1990, 31, 6613.
CH2(C02Eth , I 2 , 2 h
B"&
- P:;It
KzCO3, reflux Bu 39% tricapylMeNC1 T6ke, L.; Szab6, G.T.; Hell, Z.; T6h, G. Tetrahedron Leff.,1990, 31, 7501. 0.75 Dibal , PhH RT,lh
54% 77% ee
Dauben. W.G.; Hendricks, R.T.; Luzzio. M.J.; Ng, H.P. Tetrahedron Lett., 1990, 31, 6969. CFC13 , T i c 4 , 0°C 0.33 ;-
Php Me LiAIH4,30min Me Burkholder. C.R. J. Org. Chem., 1990, 55, 589.
F
85%
110
Compendium of Organic Synthetic Methods, Vo18
Br
Section 74F
TCNE , THF -1O"C, I h
wOMe
OMe
NCX::e NC C N
88%
Lee, J-Y.; Hall, H.K. Jr. J, Org. Chem., 1990, 55, 4963. 1. (+)-TMTA , MS 4A 2. CH212, Zn-Cu ,ether reflux, 24 h
Bu
B(oH)2 3. H202.2N KHCO3 TMTA = N,".N-tetramethyI
THF
-
B " q O H 91%ee
tartaramide
67%
h i . T,; Mineta, H.; Nishida, S . J. Org. Chem., 1990, 55, 4986.
r
I
Me
& CFCH ,PhH , 5 % KOH
M e CI
dibenm-18-crown-6
RT.Sd
Sheu.;Yen, C-F.; Chan, Y-L.; Chung, J-F. J. Org. Chem., 1990, 55, 5232.
o/
Ph
Zn , THF , CF2Br2
RT , overnight
F
96%
yields range from 496% with various alkenes
Q!JbaXLk Wojtowicz, H.; Burkholder, C.R. J. Org. Chem., 1990, 55, 5420.
d+
CH2N2 ,PdC12(PhCN)2 CHzClz - ether
OH
10°C + RT
c
74%
also used to convert allylamines to aminomethyl cyclopropanes Tornilov, Yu.V.; Kostitsyn, A.B.; Shulishov, E.V.; Hefedov. Synthesis, 1990, 246.
0.m
1. CO , THF
SiMe3 15"C, 2 h =c=( 2. ?-BuMe$iCI c. M % s i v OSiMe2t-Bu OSiMe,r-Bu Li HMPA ,-78°C 59% 15% Ryu, I.; Hayama. Y.; Hirai, A.; Sonoda, N.; Orita, A.; Ohe, K.; Murai. S , J. Am. Chem. Soc., 1990, 112, 7061.
4SiMe3
+
111
Cyclopropanations of Alkenes
Section 74F
*$ 1.
Me3P
@
APh
0-K+ Mew ,THF ,-6OT
Ph
60h
2.12, THF , -78°C
0
PF60
Tjaden, E.B.;
70%
J. Am. Chern. SOC., 1990, 112, 6420. -C1
1. Mg , THF 2. aa. NHLI
-
1OH
(3 2) 75% Akhmedov, M.A.; Akhmedov, I.M.; Mustafaeva, Z.G.; Sardarov, I.K.; Kostikov, R.R.; Musaeva, Kh.E. Zhur. Org. Khim., 1990, 26, 1257 (Engl., p. 1087).
& Me
Bu
BuQ,Me FCO),MeG'" OMe
-*'
THF, 100°C
I
71%
Me
Harvev. D.F,; Lund, K.P. J. Am. Chern. SOC.,1991, 113, 8916. Harvev. D.F,; Lund, K.P.; Neil, D.A. Tetrahedron Letr., 1991, 32, 6311. Kh2(5S-MEPY)4 , 25°C 74% (88% ee) Dovle. M.P,; Pieters, R.J.;Martin. S.F,; Austin, R.E.; Oalmann, C.J.; Muller, P. J. Am. Chern. SOC., 1991, 113, 1423.
\
90%
Kulinkovich, O.G.; Sviridov, S.V.; Vasilevskii, D.A.; Savchenko, A.I.; Pritylskaya, '1,s.Zhur. Org. Khim., 1991, 27, 294 (Engl., p. 250).
EtC0,Me
1 . 2 eq. EtMgBr , 10%Ti(OiPr)4 ether
t
hEk 76%
2 . 5 % aq. H2SO4,5"C OH Kulinkovich. O.G,; Sviridov, S.V.; Vasilevskii, D.A. Synthesis, 1991, 234.
112
Compendium of Organic Synthetic Methods, Vol8
Section 74F
2 CBrzFZ, CHZBr2,27 h 2 KOH (60%aq)
BufiHS04 Balcerzak, P.; Fedorjhski, M.;
F
F
70%
J. Chem. Soc., Chem. Commun., 1991, 826. n
1. Me N-NeLi
, 2 B,,L~
P h d , Ph Ph>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<
Me02C&0
c
Me02C
94%
Katz.;Yang, G.X-Q. Tetrahedron Lett., 1991, 32, 5895. Me?
C02Me
Br
1. t-BuOK , THF -7OOC. 100 min 2. 1N HCI ,-70°Cd
(75:25 Z E )
Br 12%
88%
Duhamel.; Peschard, 0.; PIC, G . Tetrahedron Lett., 1991, 32, 4695.
\ro
-0
Y
+
Jy
Ph
Ph
O
Ph
(89% dr)
major
Davies.;Cantrell, W.R. Jr. Tetrahedron Lett., 1991, 32, 6509. Davies.;Hu, B. Tetrahedron Lett., 1992, 33, 453. Br
PhMgBr , 2 Sd, THF - HMPA -
-co,Et
-
pc,”,”
Fukuzawa. S.; Niimoto, Y.; Sakai, S. Tetrahedron Lett., 1991, 32, 7691.
NO2
OH
NZCHC02Et , PPh3 PhH , RT
t
A NO2
n-C4Hg
(10:l trans:cis)
Yu. J.;
Falck.;Mioskowski, C . J. Org. Chem.. 1992, 57, 3757.
90%
82%
91 %
114
Compendium of Organic Synthetic Methods, Vo18
TI1F WHs) , - 7 8CH2I2 T + RT
Me3Si
Section 74F
,,%+
Me$;%
H
OH
HO
HO
(1
1.3)
Lautens.;Delanghe, P.H.M. J. Org. Chem., 1992, 57, 798.
.
aq. NaOH heat
0.i.
84%
.N-TS
H?
HO
81%
Me
M o u l i n a ; Charpentier, P.; Bats, J-P.; Nuhrich, A.; Lamidey, A-M. Tetrahedron Lett., 1992, 33, 487. 1. Zn ,THF ,reflux 2. CISiMe$-Bu
I
OSiMezt-Bu
0
564
Yasui, K.; Fugami, K.; Tanaka, S.;~amaru.Y.; Ii, A.; Yoshida, Z.; Saidi, M.R. Tetrahedron Letf., 1992, 33, 785, 789.
Ph
0.03% C ~ ( P P ~ ~ ) ~ R U [ H ~ Cph ~B~HI~]
NzCHCOzEt , 6OoC,4 he
86% (cktrans = 0.69)
Demonceau.A.; Saive, E.; de Froidmont, Y.; Noels, A.F.; Hubert, A.J. Tetrahedron Lett., 1992, 33,2009.
Ph H
MeS
1. BuLi
2. PhSqCl
3. BuLi,-7g0C
H M e w M e ph.
79%
(88% dr) Krief.;Hobe, M.; Dumont, W.; Badaou, E.; Guittet, E.; Evrard, G. Tetrahedron Lett., 1992, 33, 3381. I(rief.;Hobe, M. SynLefl, 1992, 317.
Eto2Cv l.NaH,THF 2. 1,
CO2Et
3. THF ,reflux
E t o 2 C A I EtO2C
Beckwith, A.L.J.; Tozer, M.J. Tetrahedron Lett.. Z992, 33, 4975.
81%
Section 74F
Cyclopropanations of Alkenes
115
Et2Zn. CH212, -23°C. 5 h
CHzC12-10% hexane
0
P h A O H
Ph
*
NHS02Ph
Takahashi, H.; Yoshioka, M.; Ohno, M.; &hyj&&
OTs
%
AC S - H
c
Bu
Tetrahedron Lett., 1992, 33, 4103.
0 1. T ~ H N N A C I
, p m q
NEt3. CH2C12 2. RhZ(SS-MEPY)d ,C112CI2
--
0 %
74%
(77% ee)
MEPY = tetrakis[methyl-2-pyrrolidinone-5S-carboxylate~
Martin. S.F,; Oalmann,C.J.; Liras, S. Tetrahedron Lett., 1992, 33, 6727.
(101
E:Z)
Harvev. D.F,; Lund, K.P.;Neil, D.A. J. Am. Chem. SOC.. 1992, 114, 8424. jiarvev. D.F; Brown, M.F. Tetrahedron Lett., 1990, 31, 2529.
phmMe
4Ph , Zn(Hg) , ether c
59%
ClMe2SiCH2CHzSiMezCl
(11:l cktrans)
Motherwe 11. W.B.; Roberts, L.R. J. Chem. SOC.,Chem. Commun., 1992, 1582. 1. EtzZn , PhMe 2. diethyl tartrate
Ph-OH
3. Et2Zn ,CH&
vkaji, Y.; Nishimura, M.;
64%
(2:l E:Z)
Pyo, S.; Skowron, J.F. 111; QlaJK.
OH
75%
Tetrahedron Lett., 1992, 33,2515.
'
5 eq. LDA ,THF -78°C
OH (68% ee)
NHSqPh
,"3'
>
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<
Me Ph
qum.
Chan, Y.N.C.; Meyer, D.; Qsborn. J.A,J. Chem. SOC., Chem. Commun., 1990, 869.
,OH
L
2% R U ~ ( C O PhH ) ~ ~ ,, 4 h 100°C, CO (20 Kg/cm2)
N.H & Ph
Ph
quant.
Akazome, M.; Tsuji, Y.;m a b e . Y. Chem. Lett., 1990, 635.
Ph,N.
l.Zn(BH& , ether 0°C -+ RT
H
98% 2.2NNaOH Ph FotsukifL; Yoshimura, N.; Kadota, I.; Ushio, Y.; Ochi, M. Synthesis, 1990, 401.
Me3Si-
Ph,N.
Ph
B-Q
1. n-C,H,-CH=NMe THF ,65"C, 72 h
Me3Si
2.3w0HzO2,lM NaOH
n-C3H7
3.2M HCI ; 2M NaOH
A NHMe
53%
Guyot, B.; Pornet, J.; Miginiac, L. Synrh. Commun., 1990, 20, 2409.
HPhPOzH , 120"C, DMSO
*
PhCH,NH,
U S y n t h . Commun., 1991, 21, 1425.
1. BuLi 2. CpzZrMeCl 3.60"C. THF , 12 h
fr
4-
Q
*
1. BuLi , THF
H
28% with BuBr Epline. G.A,; Kumar, A. SynLett, 1991, 347.
73%
% a -
5. MeOH Coles, N.; Whitbv. R.J. ; Blagg, J. SynLert, 1990, 271.
2. BuOMs
PhCH,NMe,
c
92%
Bu
75%
148
Section 97
Compendium of Organic Synthetic Methods, Vol8
N.OMe
A! Ph
BFyOEt2 , PhLi , PhMe -78°C
H Uno.;Terakawa, T.; &uukiJL
S y d e t t , 1991, 559.
t-Bu
Clostridia thermoaceticum ,0.033 M 0.1 M phosphate buffer (pH 8.5)
t-Bu I
Ph JNHoMe 59%
I
NHoH
0.3 M sodium formate, 5 h * 80% 0.001 methyl viologen ,40°C Braun, H.; Schmidtchen. F.P,; Schneider, A.; Tefrahedron, 1991, 47, 3329.
SiMe3 Ph p N A
%Me3
-
1.200"C. neat. 1 h 2. TMSCI ,MeOH 0°C , 1 h
Palorno.;Aizpurua, J.M.; Garcia, J.M.; Legido, M. J. 524.
4-
M e 0 0 Pb(OAc),
\ /
NH2
-
Cu(OAc)z, CH2C12,2 h
m
'+Ph
65%
SiMe3
Chem. Soc., Chem. Commun., 1991,
4N.k
95%
OMe
Barton, D.H.R.; Donnellv. D.M.X.; Finet, J-P.; Guiry, P.J. J. Chem. Soc., Perkin Trans. I, 1991. 2095. 1. HSiCI, , BF3*OEt2
PhH
O N H P h 2. KOH ,aq. EtOH
81%
Okamoto.;Kato, S. Bull. Chem. Soc. Jpn., 1991, 64, 3466. 1. KO11 , DMSO
'N
H
3. Pd(PPh3)d , KOAc DMA , 130"C, 10 h
Kozikawski.,Ma, D. Tetrahedron Lett., 1991, 32, 3317.
' N 77%
/
Section 97
Amines from Amines
H3BO-j. 180°C. 1 h t
COZEt Delbecq, P.; Bacos, D.; Celerier, J.P.; €&nunet.
HO
149
& N
95%
G,Can. J. Chem.. 1991, 69, 1201.
DEAD,PPh3.3 h CH2C12
P
CNHPh
M N\
e
Ph
80%
Bemotas. R.C,; Cube, R.V. Tetrahedron Lett., 1991, 32, 161.
7R%
H
Jackson, W.R.; Nilsson, Y. Tetrahedron Lett., 1992, 32, 1093.
;-
1 . 3 eq. BuLi-2 1-BuOK
86%
H
H Naruse, Y.; Ito, Y.;
Me,Si
J. Org. Chem., 1991, 56, 2256.
Nw".
Ph
1. PhMe, reflux, 5 h 2. H 2 0
*
Ph
Ph
Ohno, M.; Miyata, H.; Komatsu. M.; Ohshiro. Y,Tetrahedron Lert.. 1991, 32, 5093.
"OH
Ph
J!
TSCN, mt3, C C ~ t
0°C
/
A
Ph Ph Boeer.;Corbett, W.L.J. Org. Chem., 1992, 57, 4777.
TS
Ph
69%
hv ,MeOH , 2 . 5 h 1% H2S04
*
Q ~ L L LTetrahedron Lett., 1991, 32, 5235.
73%
53%
150
Compendium of Organic Synthetic Methods, Vol8
0: 3 I
NHz
Section 97
, 5 % PdC12
5% PPh3, HMPA 3 eq. NaHC03,l d 14OOC
h o c k . R.C.; Kuo, M-Y. Tetrahedron Lett., 1991, 32,569.
62%
Uno. H,; Okada, S.; Ono, T.; Shiraishi, Y.; Suzuki. H. J. Org. Chem., 1992, 57. 1504. /= N-t-Bu
Me0
1. sec-BuLi
2. aq. NH4CI
Me0 >99%
Sielecki, T.M.; Mevers. A.1, J. Org. Chem., 1992, 57, 3673.
Me
Pearson.;Postich, M.J.J. Org. Chem., 1992, 57, 6354.
(73%ee, S)
Kawate, T.; Nakapawa.; Kakikawa, T.;
Tetrahedron Asymmetry, 1992, 3,227.
L6pez-Alvarad0, P.; Avendafio, C.; Mentndez, J.C. Tetrahedron k i t . , 1992, 33,659.
Section 97
Amines from Amines
Me phA
F
151
Me
C S 2 , MeCN
.Me
*
OH
P h A N . M e 87% H
Schwartz. Me&; Gu,J.; Hu, X. Terrahedron Lett., 1992, 33, 1687.
@HOH
2.EtMgBr 1. acetone i
3. cs2
Me0
Me0
OMe
Schwartz.;Hu, X. Tetrahedron Lett., 1992, 33, 1689. 0.1 BuLi ,THF
Ph
NHMe
Ph
Ph
Fujita, H.; Tokuda.;Nitta, M.;
84%
OMe
A - L Ph N
99%
Me
Tetrahedron Lett., 1992, 33, 6359.
hv , iPrOH .'DCN
+ (97
3)
90%
pandev.;Reddy, G.D. Tetrahedron Lett., 1992,33,6533. 1 . 2 eq. H 2 0 2 , MeOH
Murahashi.; Naota, T.; Miyaguchi, N.; Nakato, T. Tetrahedron Lett., 1992, 33, 6991.
Izumi.;Yokota, T. J. Her. Chem., 1992, 29, Ph7 N =CHPh
1085.
0.5%R u C ~ ~ ( P P ~82°C &, 5% KzCO3, iPrOH , 1 8 h
*
Ph--\ H'
Ph NJ
Wmg, G-Z.;BBCkVall. J -E.J. Chem. SOC.,Chem. Commun., 1992, 980.
93%
152
Section 97
Compendium of Organic Synthetic Methods, Vol8
N
A
x2
1.0.2%Rh(COD)(Et-DUPHOS)+ OTf ' iPrOH, ~ H2~(4 a m ) ~ ~ b
Ph
quant.
Ph
2.SmI2
(89% ee , S)
Et-DuPHOS =
Burk. M.J.; Feaster, J.E. J. Am. Chem. SOC.,1992, 114, 6266. 5%-
- XTj-X
&NAPh
, 2 BuLi , PhSiH3
H,(2OOOpZ)
68%
(58% ee)
X = l,l'-binaphth-2.2-diolate
Willoughby, C.A.; E U & m L S L J. Am. Chem. Sac., 1992, 114, 7562.
2% NiSO4, K2S208 NaOH ,H20-CH2C12
E
N
.
m
RT, 3.5 h
N
87%
Yamazaki. S, Chem. Lett., 1992, 823.
CuBryLiOl-Bu ,THF
E
N
.H
RT , 2 0 min
*
W
N
89%
Yamaguchi, J.; u e d a . T. Chem. Leu.,1992, 1933.
TOgO.;Miyagawa, N.; %&@mud. Chem. Lett., 1992, 1677.
MeCH=N-NMe2
1. EtI 2. KOH ,MeOH
*
EtNMe,
a i t h . R.F.; Marcucci, J.L.; Tingue, P.S. Synth. Commun., 1992, 22, 381.
57%
Section 100
153
Amines from Halides
d$ 0"""' 1. t-BuOOH , PhH
RuC12(PPh&
2.TiC4,
66%
he
Murahashi.: Naota, T.; Nakato, T. SynLerr, 2992, 835.
SECTION 98: AMINES FROM ESTERS
Ph-
OAc
MesSiN3, 50°C, 2h Pdz(dba13 , 4 PPh3
*
Ph85%
Safi, M.; Fahrang, R.: Sinou, D. Tetrahedron Lett., 1990, 31, 527.
SECTION 99:
N,
AMINES FROM ETHERS, EPOXIDES AND THIOETHERS PhNH2, Ti02,25O-3OO0C
N
Ph
96% selectivity
Hareis, D.C; Shubkin, R.L. Tetrahedron Lert., 1990, 3J, 2991. AICI:, ,AcOH ,20 h NH;?OH*HCI,reflux
Jun. J-G,; Shin, H.S.Tetrahedron Lett., 1992, 33, 4593.
SECTION 100: AMINES FROM HALIDES AND SULFONATES
OTBS
+C02~e 6Ms
NaN3-CuI
HMPA.4h
OTBS
A C O 2 M e N3
(85
with NaN3 , DMSO (0 yamamot0.y.: Asao, N.J. Org. Chem., Z990, 55, 5304.
+
OTBS
b C 0 2 M e
63 15)
100)
86%
42%
154
Section 100
Compendium of Organic Synthetic Methods, Vo18 0.1 AgI ,LiN(SiMe3),
54%
N(Si'e3)2
THF ,reflux, 6 h
Murai.;Yamamoto, M.; Kato, S. J. Chem. SOC., Chem. Commun., 1990, 789.
NaN(CH0)2 Yinelin.
1. BuOTs , MeCN , 120°C 2. HCl
BuNH**HCl 88%
K; Hongwen, H. Synthesis, 1990, 122.
NEtz
51%
Matsumoto.; Hashimoto, S.; Otani, S. J. Chem. Soc., Chem. Commun., 1991, 306. EtzHNHN3, DMF Yokoyama, H.; Ishikawa, T.; Niwa, N.;
&&Q&
Tetrahedron Lett., 1991, 32, 663.
Saito.;Takahashi, N.; Ishiwawa, T.; Moriwake, T. Tetrahedron Lett.. 1991. 32, 667. I. Bn2NH ,K2CO3 diglyme , 14OOC
Br Purchase, C.F. 11.;
2. HCl(g),iPrOH 3. NHdHC02. 10% PdC MeOH .6S0C J. Org. Chem., 1991, 56, 457.
pyrrolidine ,50°C 6 kbar , THF
-NH* 72%
0 2 N O N 3
*
Ibata.;Isogami, Y.;Toyoda, J. Bull. Chem. SOC.Jpn., 1991, 64, 42. 1. NaNq ,PhH-DMF ,reflux 2. P(OEt)3
Ph-
Br
b
Ph/\/
91%
NHBn*HCl
3. PhCHO 77% 4. N a b , NaOH 5. aq. HCI Gajda, T.; Koziara, A.; Osowska-Pacewicka, K.; Zawadzki, S.; Zwierzak. A, Synth. Commun., 1992, 22, 1929.
155
Amines from Hydrides
Section 101
SECTION 101: AMINES FROM HYDRIDES 1. PhI(OZCCF3)z (CF3)zCHOH
MeoG Me
2. Me$iN,
u; Tohma, H.; Inagaki, M.; Hatanka, K.; Yakura, T. Tetrahedron Lett., 1991, 32, 4321. 1. PhNHz , Zn , AcOH
70°C
NHPh
*
2.NH40H
85%
MiCoviC, I.V.; IvanoviC, M.D.; Piatak, D.M.; BojiC, V.D. Synthesis, 1991, 1043. MeNOzCH3S03H. 16 h 75OC
*
Ph)=N.oH
Me
33% z
75%
(E+Z)
Coustard, J-M.; Jacauesv. J -CL Violeau, B. Tetrahedron Lett., 1992, 33, 8085.
Maenos.; Lacour, J. J. Am. Chem. Soc., 1992,
114, 767.
SECTION 102: AMINES FROM KETONES 0 phA M~
1. PhNHz ,CIIzCI2
TiC14, EtN(iPrh
2. NaCNB%
c
Ph
YNHPh
Me
94%
Barney, C.L.;Huber, E.W.; McCarthv. J. R, Tetrahedron Lett., 1990, 31, 5547.
0
n-C3H7NH2, DCE AcOH , N ~ B H ( O A C ) ~ 3h also works with
aldehydes
NH~z-C~H~ 88%
Abdel-Maeid.;Marvanoff.;Carson, K.G. Tetrahedron Lett., 1990, 31, 5595. A b d e f - w:Mayanoff, C.A. Syntett, 1990, 537.
Compendium of Organic Synthetic Methods, Vol. 8
156
Section 102
1. MeJ NOz , LDA, THF , -78°C
0 MeKn-C7H,5
2. A c ~ O 3. H2 M/A1203. MeOH
MeQn-C7H,,
c
H
53%
H2 with Pt02 and treatment of m i n e with pTsOH leads to a pyrroline Miyashita, M.; Awen, B.Z.E.; Yoshikoshi. A. Chern. Lett., 1990, 239.
aNHz 1.33% KOHEtOH reflux, 2 h
Ph-Me 0
+
CHO 2. AcOH
76%
LL Org. Prep. Proceed. Int., 1991, 23, 23.
Akula, M.R.; Wolowyk, M.W.; Knaus.
OH
P
h
0
1. Ph"'NH2 2. LiAIH4-AlC13 3. PCVC ,H2
y Co2H
-
BniO1
Mevers. A.I.; Burgess, L.E. J. Org. Chem., 1991, 56, 2294.
41%
&
Hz , Pd-C , EtOH
=
N02
N H
Me
Me
Janowitz, A.; Vavrecka, M.; Hesse. M, Helv. Chim. Acta, 1991, 74, 1352.
1.
,BH3
Me'
BO
THF
2. PPh3, HN3 , PhMe DEAD, 0°C + RT 3. PdC ,TFA
81%
Chen, C-P.; Prasad.; Repic, 0. Tetrahedron Letr., 1991, 32, 7155.
0 !hrh&&;
t-BuNH2, TiCl4-C
(87% ee)
N-t-Bu
Larsson, U.; Hansson, L. Acta Chem. Scand., 1992, 46, 1211.
75%
157
Amines from Nitriles
Section 103
1
~ K S 1H1
CCl,
1. 0 0 B0. H
2.
sh, PhMe
Ph
-6OOC
3. NaN3, DME ,aq. NaOH
YH2
n-C5HCC02H
4. 1130'
80%
5. H 2 , I'd-C
(95% ee)
u; Link, J.O. J. Am. Chem. SOC.,1992, 114, 1906.
Related Methods: Section 94 (Amines from Aldehydes)
SECTION 103: AMINES FROM NITRILES
%
CN
cat. Coz(CO)8 , PPh3 HSiMe3 , CO (atm)
N. %Me3
&Me3
PhMe , 1OO"C, 20 h%
quant.
Murai.T,; Sakane, T.; Kato. S . J. Org. Chem., 1990, 55, 449.
1. iBuzAlH 2. BuLi , THF
Ph-CN
Bu
3. NH4C1, NH40H*
Andreoli, P.; Billi, L.; Cainelli, G.; 1990, 55, 4199.
.
5% Rh on A1203
Ph--(
NH2
98%
;Martelli, G.; Spunta, G. J. Org. Chem.,
-
PhpNAPh
Ph-CN Hz ,AcOH H 85% G a l a , A.; de Mendoza, J.; Prados, P.; Rojo, J.; Echavarren, A.M. J, Org. Chem., 1991, 56,452.
PhCN
1. BH3 2. BuLi , hexane
-80°C. 2 h
t
95%
m;Hachisuka, C.; Ito, K. J. Chem. SOC.,Perkin Trans. I, 1991, 1767.
Itsuno.;Hachisuka, C.; Kitano, K.; Ito, K. Tetrahedron Lett., 1992, 33, 627. n-C1 iH23CN
3 eq. MeCeCl2 , -65'C
5h
J. Org. Chem., 1992, 57, 4521.
NH2 n-C 1 IH,3 Me 64%
158
Methods, Vol. 8
Compendium of Organic S;.....,yz
Section 104
1. NaBH(4-,)(02CEt),
PhCN
PhdNH2 Bu
2.2 eq. BuLi ,80°C, 1 h
59%
Itsuno.;Hachisuka, C.; Ushijirna, Y . Synrh. Commun., 1992, 22, 3229. SECTION 104: AMINES FROM ALKENES 1. BH? 2. [BuNH2-NaOCIl, 0°C -+RT
67%
3. aq. HCl (pH <1) 4. aq. NaOH
Kabalka. G.W,; Wang, Z. Synth. Commun., 1990, 20, 231.
Ph
PhI=NTs , MeCN 10%Cu(acac)2
I
/
Ph
1
N- TS
a D.A.; F a d , M.M.; Bilodeau, M.T. J. Org. Chem., 1991, 56, 6744.
a
95 %
MeNHpHOAc MeOH ,reflux
21h * W N H M e 82% Cliffe.;Ifill, A.D.; Mansell, H.L.; Todd,R.S.;White, A.C. Tetrahedron Lett., 1991, 32, 6789.
d
Ph
Mn (salen)
c
PhI=NTs
Ph
A
N
'Ts
46%
OConnor, K.J.; Wey, S-J.; Burrows. C.J. Tetrahedron Lett., 1992, 33, 1001. 1. MesSiOTf CH&12 I
-14°C 2. HN(OMe)2
N- OMe
3. IMNaOH
Vedeis.; Sano, H. Tetrahedron Lett., 1992, 33, 3261.
64%
MqSi f i N * OMe
cat. TFA ,CHICll Bn
J&ukE.
*
O z N W - B n 71%
Tetrahedron Lett., 1992, 33, 6607.
1. H! 3 CN
-m N'H2
50%
SH,MeOH
2*
25°C SH Tetrahedron Lett., 1992, 33, 3599. ~~
Cho, C-G.; REVIEWS:
;-
159
Amines from Miscellaneous
Section 105
"An Overview of the Total Synthesis of Pyrrolizidine Alkaloids via [4+1] Azide-Diene Annulation Methodology" Seoane, G.; Price, J.D.; Gadamasetti, K.G. Syntett, 2996, 433.
SECTION 105:
Boivin, J.; Fouquet, E.;
AMINES FROM MISCELLANEOUS COMPOUNDS
Tetrahedron Lett., 1990, 31, 85.
Ph b
Ph
p
h
81%
NO H Jevaraman. R Ravindran, T. Tetrahedron Lett., 1990, 31, 2787. 1. DME:, 12OoC, 17 h 2. PhH, NH&I, 4 h 18
3. H2 ,Pt02 ,ether 25°C
Me
3) (1 Heidt, P.C.; Bergmeier, S.C.; Pearson. W.H. Telrahedron Lett., 1990, 31, 5441. bakers yeast, pH 5 12 h , 22°C
Gibbs.;Barnes, D. Tetrahedron Lett., 1990, 31, 5555.
Me
28%
Compendium of Organic Synthetic Methods, Vol8
160
Section 105
1. PhH ,reflux, 12 h 2.NaBH4,MeOH 0°C , 1 h Pearson.; Lin, K-C. Tetrahedron Lett., 1990, 31, 7571.
N3
0
1 . 2 eq. AlI3 , MeCN , 3 h reflux
N.
2. Na2S203, H20
t
Ph
Ph
96%
Ph-N.
t
91%
Ph
Konwar, D.; Boruah, R.C.; S a n d h u . S y n t h e s i s , 1990, 337. MeOH , reflux
Ph-N3
Ph-NH2 BH4
CH$kle?
Kabalka.;Wadgaonkar, P.P.; Chatla, N. Synrh.
1 1'
1.
-N3
94%
Commun., 2990, 20,293.
BC12
,DCE
2. H 2 0 3. KOH
-N
+
H
(>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
l
80%
ETHERS, EPOXIDES AND THIOETHERS FROM ALDEHYDES B
n
O
A
0s PhCHO
6, OBn
--
Bn
p%
50% NaOH ,cat. BnEt3NHCI Ph Ph CH2C12 , 0°C 53% (60%ee) Breau, L.; Ogilvie, W.W.;Purst.&Tetrahedron Len., 1990, 31, 35. @
Ph,As
-OH
XO
Wmg, W-B.; Shi.; Li, Z-Q.;
PhCHO ,MeCN €W*AI@q
-
Ph 78%
- Tetrahedron Lett., 1991, 32, 3999.
Section 124
187
Ethers from Aldehydes
,iBu2Te
JBr
PhCHo
cs2CO3, THF/ether/H20c 5O"C, 19 h
ph& (71:29
75%
cis:trans)
- Tetrahedron Lett., 1990, 31, 7657.
Zhou, Z-L.; Shi, L-L.;
0 0 Ph2Te-CH3 BPh4
1. LiTMP ,THF , -78°C c
2. PhCHO -78°C + RT
also reacts with ketones Shi, L-L.; Zhou. Z-L.: Huang, Y-2. Tetrahedron Lett., 1990, 31, 4173.
h CHO
1. P ~ ~ ATHF s , , -78°C iPr3SiOTf
2. KNTMS2, -78°C 3. PhCHO , -78°C 4. TBAF , -78°C + RT Kim. k, Kim, Y.G.Tetrahedron Lett., 1991, 32, 2913.
PhCHO
+
ph
A OSiMe, -
P h + OSiMe,
R Ph
hv
(>95 Bach. T. Tetrahedron Lett., 1991, 32, 7037.
:
Fire3
Ph
5)
39%
1. n-C3H7CHO, PhSH ,H+
2. BuLi * 4 P h 3.MeI Ph 46% H 4. PhCHzMgX M t z k v . A.R.; Perumal, S.; Kuzmierkiewicz, W.; Lue, P.; Greenhill, J.V. Helv. Chim. Ada, 1991, 74, 1924.
Me Me+Co2Me
SiMezPh
Bn0,CHO
,- 7 8 0 ~
CFyOEt2, CHg12
15h
Panek. JS,; Yang, M. J. Am. Chem. SOC.,1991, 113, 9868.
85%
(30:l 4.5-syn:anti ; 96% dr)
188
Section 128
Compendium of Organic Synthetic Methods, Vo18
r-BuOSiMe3 , Me3SiH PhCHO
TMSI ,pentane -78°C + RT
*
PhCH,Ot-Bu
71%
Hartz, N.; Surva Prakash. G.K.;W, (3.4,SynLett, 1992, 569.
ysiMe3 ,()
PhCHO
-I
20% Me3SiOTf OSiMe3 CCl4,2O"C
Ph
85%
Mark6 I.E.; Mekhalfia, A. Tetrahedron Lett., 1992, 33, 1799.
ETHERS, EPOXIDES AND THIOETHERS FROM ALKYLS, METHYLENES AND ARYLS
SECTION 125:
NO ADDITIONAL EXAMPLES
SECTION 126:
ETHERS, EPOXIDES AND THIOETHERS FROM AMIDES NO ADDITIONAL EXAMPLES
SECTION 127:
ETHERS, EPOXIDES AND THIOETHERS FROM AMINES 1. NaN02, HCl
c1
2. H02CH2SH
35%
Org. Prep. Proceed. lnt., 1991, 23, 198.
Yildirir, Y.;
SECTION 128:
ETHERS, EPOXIDES AND THIOETHERS FROM ESTERS
0 S
1. MeLi 2. Me1
3.Ph3SnH
0 Me
85%
Nicolaou. K.C.; McGanry, D.G.; Somers, P.K.; Kim, B.H.; Ogilvie, W.W.; Yiannikouros,G.; Prasad, C.V.V.; Veale, C.A.; Hark, R.R. J. Am. Chem. SOC..1990, 112, 6263.
Section 129
Ethers from Ethers
189
qSePh
PhSeSePh ,THF , 15 h
OAC
2.5 eq. Sm12 , 5% PdCI;! c 20% PPh3,25'C
84%
Fukuzawa.: Fujinami, T.; Sakai, S. Chem. Left., 1990, 927. fO y OPh 0
5% Pd(0Ac)z. THF 20% PPh3 ,25"C, 1 h
c
=foPh
87%
Larock, R.C.; Lee, N.H. Tetrahedron Left., 1991, 32, 6315.
& !!
SEt
2 eq. NiC12.6 HzO 2 &.Zn* ,-8eq.-PPh3
DMF , 2 3 T , 2 0 h
SEt
*
73%
W~~LJL Chianelli, E . ; D. J. Chem. Soc., Chem. Commun., 1991, 627.
S
n-C ~
O
H SMe ~
3 eq. DBH , CH2Cl2 1 py
~
O
~
L-
n-C
CF3
80%
DBH = 1,3dibromo-5,5-demethylhydantoin Juroboshi, M.; Suzuki, K.; Hivama. T. Tefrahedron Lett., 1992, 33, 4173. Pdz(dba)s, dppb , PhOII THF,60T, 12h
0
O K OMe
-0Ph
75%
Goux, C.; Lhoste, P.; SiwuJL SynLetf, 1992, 725. Goux, C.; Lhoste, P.; D. Tetrahedron Left., 1992, 33, 8099 [with thiols].
mu.
SECTION 129: ETHERS, EPOXIDES AND THIOETHERS FROM ETHERS, EPOXIDES AND THIOETHERS
0
1. 5% Pd(0AC)z 3 KOAc , DMF
Bu~NCI,80°C
Meoa, Me0
m'
2.4% Pd(0Ac)z 9% PPh,, MeCN 2 A g K 0 3 , 8o°C 3. H, ,PtOz ,EtOAc , IWmin
Larock.;Gong, W.H. J. Org. Chem., 1990, 55, 407.
68% overall
190
Compendium of Organic Synthetic Methods, Vo18
Nambu, Y.;
Section 129
Tetrahedron Lett., 1990, 31, 1723.
Eisch.;Galle, J.E. J. Org. Chem., 1990, 55, 4835. e- , S, , Pt electrodes
37%
OMe Le Guillanton, G.; Do, Q.T.: Simonet, J. J. Chem. Soc., Chem. Commun., 1990, 393. t-BuOK , 18crown-6 PhH ,reflux, 4 h
Duldre, J-P.; Rodriguez, J. Synlh. Commun., 1990, 20, 1893. iBu2AlSePh , PhMe Nishivama. Y,; Nakata, S.; Mamanaka. S, Chem Lett., 1991, 1775. SmI2-MeCN ,MeCN t-BuOH, HMPA
Ph with mines as well as ethers Ujikawa, 0.; Yamaguchi, M. Tetrahedron Len., 1991, 32, 1737. Zn(BH& on Si02 THF , -lO°C, 8h b a l . V&;
Me
*
g
80%
Me
Singh, S.P.; Dufour, C.; Michoud, C. J. Org. Chem., 1991, 56, 5245.
191
Ethers from Halides
Section 130
EgSiH , TMSCl
-
Ph-SEt
4
83% InC13, CH2Cl2 , RT Mukaiyama, T.; Ohno, T.; Nishimura, T.; Han,J.S.; Kobayashi, S. Bull. Chem. Soc. Jpn., 1991, 64, 2524.
SEt
Ph
Ph
BnOTMS , Et3SiH , O T 5% SbCIyAgSbFs, 2 h
Ph Ph*oJph
w
83%
Harada, T.; Mukaivama. T, Chem. Lett.. 1992, 1901.
SECTION 130:
ETHERS, EPOXIDES AND THIOETHERS FROM HALIDES AND SULFONATES OBn
+
*
F
MqGaCI ,MeCN
BnO
90 h
80)
,-
quant.
Koide, K.; Ohno, M. Tetrahedron Lett., 1990, 31, 2435.
Fllssph , phoph 25OoC, 8 h
Ph-I
Ph-S-Ph
quant.
Wang, Z.Y.; Hay, A.S. Tetrahedron Lett., 1990, 31, 5685.
Ph-
Br
PhqSn-Te-SnPhl ,45"C 4 CSF , CD3CNt 24 h +.
Ph,Te,,Ph quant.
Li, C.J.;
Tetrahedron Lett., 1990, 31, 6291.
BnOH ,t-BuOK , TDA-1 140°C, 2 h
98% TDA-1 = see J. Org. Chem., 1985, 50, 3717 Lgupv. A,; Philippon, N.; Pigeon, P.; Sansoulet. J.; Galons. H. Synth. Commun., 1990, 20, 2855.
Section 130
Compendium of Organic Synthetic Methods, Vol8
192
Hengchane. C. ; Zhenzhong, L.; Wei, L. Synrh. Commun., 1990, 20, 3313.
pe Kimpe. N,; Stevens, C. Tetrahedron, 1990, 46,6753.
0 0
c1 OTf Pd(OAc)2.(R)-BINAP iPr2NEt. W H , 2 2 h
Ozawa, F,; Kubo, A.; b
o....o 0
/
c1 + %
/ 17)
(83
shi. T, J. Am. Chem. SOC.,1991, 113, 1417.
c1
86%
J. Org. Chem., 1991, 56,3739.
Kitamura.; Kabashima, T.;
Se
3%
94%
1. CO (5 am), D B U , HzO MeCN ,8O"C, 1 h
*
Bu-Se-Bu
75%
2. BuCl , 80°C, 1 h pishivma. Y,; Katsuura, A.; Negoro, A,; Hamanaka S.; Miyoshi, N.; Yamana, Y.;Ogawa, A.; Sonoda. N.J. Org. Chem., 1991, 56, 3776. NaOMe ,DMF ,reflux 10% CuBr ,30min Keegstra, M.A.; Peters, T.H.A.; Brandsma. L.Tetrahedron, 1992, 48,3633. S(MgBr)z, ether
Br
U
S
-
86%
Nedugov, AN.; Pavlova, N.N. Zhur. Org. Khim., 1992, 28, 1401 (Engl., p. 1103).
193
Ethers from Ketones
Section 132
NaCN ,EtOH , HzO reflux
--
OMS Pehmlow. H, ; Muler, J.; Seilz, C.: Strecker, A.R.; Kohlmann, A. Tetrahedron Lett., 1992, 33, 3607. Al2O3, Na2S
Br(CH2),Br
5
*
1.69 x l o 3 M
79%
Tan, L.C.; Pagni, R.M.; Kabalka. G.W. ; Hillmyer, M.; Woosley, J. Tetrahedron Lett., 1992, 33, 7709. Related Methods: Section 123 (Ethers from Alcohols).
SECTION 131:
ETHERS, EPOXIDES AND THIOETHERS FROM HYDRIDES NO ADDITIONAL EXAMPLES
SECTION 132:
6
ETHERS, EPOXIDES AND THIOETHERS FROM KETONES
1.12, MeOH
90%
M~ 2. PhH,NaHC03
Me COZEt see Tamara Y.;Yoshimoto, Y. Chern. Id.1980,888. , CO,Et
NazSz03 , aq.NaOH
& h i s A L Tetrahedron Lett., 1990, 31, 481.
Me3S=O+ I - , t-BuOK DMSO , RT ,16 h
86%
t
Synth. Cornmun., 1990, 20, 1193.
*At
f i S n B u 3 , 80°C, 2h p-ni titrobenzene BuZSnBrZ - HMFT
Yano, K.; Hatta, Y.; Baba.;Matsuda, H. SynLett, 1991, 555.
0
quant.
Compendium of Organic Synthetic Methods, Vol8
194
0 m.
osph
1. PhSH , HzO-BF3,O"C CHzClz, 1 min
76%
2. Et3SiH , 0°C --j RT , 3 he
G.%; Wang,Q.; Trivedi, N.J.; &uyi&&&.
Section 134
G.K. Synfhesis, 1992, 465.
Relaled Methods: Section 124 (Epoxides from Aldehydes).
SECTION 133:
ETHERS, EPOXIDES AND THIOETHERS FROM NITRILES NO ADDlTIONAL EXAMPLES
SECTION 134:
ETHERS, EPOXIDES AND THIOETHERS FROM ALKENES 1 -
PhO-
excess NaTeH p
h
O
EtOH ,reflux 24h
y
T
e
y oPh
Me Me
85% + 14% of other tellurides Barton.;Bohe, L.; Lusinchi, X . Tetrahedron Lett., 1990, 31, 93.
Adam. W.; Hadjiarapoglou, L.; Nestler, B. Tetrahedron Lett., 1990, 31, 331.
Ph
Ph\=
MnTPPCl
2
38%
TPPCl was undefined; other quinones led to higher yields
s; Ohno, M.;
Tetrahedron Lett., 1990, 31, 6039. 10% F2 in N2, H2O MeCN , 0°C , 1 min
Oo
85%
Rozen.; Kol, M. J. Org. Chem., 1990, 55, 5155.
195
Ethers from Alkenes
Section 134
PhSeSePh ,hemin-NaBH4 PhH - EtOH , 2 4 h
Ph-
Me PhA
47%
SPh
Kano. K.; Takeuchi, M.; Hashimoto, S.; Yoshida, 2. Chem. Lelt., 1990, 1381.
Jb
Lo
3% VO(acp)z, DCE 3 am 0 2 , MS 4 A ,75°C
78%
acp = 2-acetylcyclopentanone
Takai, T.; Yamada, T.; Mukaiyama, T. Chem. Leff., 1990, 1657.
NaOCl ,0.05 M , RT
Ph\=
*
2% Ni(bpy)2C12
ph\o
74%
B; Yamazaki, Y. Bull. Chem. SOC.Jpn., 1991, 64, 3185. Ph
Me \--I
aq. NOCl , CH2CIz
wMe
Ph
b
88%
0
5% Mn (salen) derivative
(84%ee , 1R2S)
Jacobsen., Zhang, W.; Muci, A.R.; Ecker, J.R.; Deng, L. J. Am. Chem. SOC., 1991. 113, 7063. Zhang, W.; Jacobsen. E.N. J. Org. Chem., 1991. 56., 2296. Lee, N.H.; Muci, A.R.; lacobsen. E.N, Tetrahedron Lett., 1991, 32, 5055.
Ph\=
1. MeOCH20S020Me. -20°C 2. MeOH t
Ph
OMe OMe
56%
Lebedev, M.Yu.; Balenkova, E.S. Zhur. Org. Khirn., 1991, 27, 1388 (Engl., p. 1214).
Ph 4
4.5 eq. ZnBrz , CH2Br2 33%
e' (Zn anode)
Durandetti, S.; Sibille. S;, Pkrichon, J. J. Org. Chem., 1991, 56, 3255. V2O5, 5 t-BuOOH
45°C , 3 h
*
0
0 45 90
Laszlo.;Levart, M.; Singh, G.P. Tetrahedron Len., 1991, 32, 3167.
196
Compendium of Organic Synthetic Methods, Vol8
COzMe P e P h
hv PhH(sunlamp) ,overnight c
&'OZMe+ SePh
Section 134
&C02Me
60%
'%
/
SePh20%
Bvers. J.H,; Gleason, T.G.; Knight, K.S. J. Chem. SOC., Chem Commun., 1991, 354.
-
yields are poor (16%) with 1-decene as a substrate Masaki.;Miura, T.; Mukai, I.; Itoh, A.; Oda, H. Chem. Lett., 1991, 1937. C8F171,EtOH , RT PhSeSePhhIaBH4 2h
63%
n-C8H 17
Kitagawa, K. Tetrahedron Lett., 1991. 32, 375.
30% H 2 0 2 , NaIlCO3
CH2Cl2, 18-crown-6
eN3 63%
m; Duldre, J-P. J. Org. Chem., 1991, 56, 469.
OMOM
OMOM
>: =-
acetone
Me
"#I
Me
(>13:1)
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
<1 min
OH
M
+
m
93% Jang, S.; Atagi, L.M.; W r . J.M, J. Am. Chem. SOC., 1990, 112, 6413.
Ph).- OSiMe, SEt
Et3SiHI CHzClz ~
TMSCI-InC13 , RT
Ph
SEt
7%
83%
Po
Mukaiyama, T.; Ohno, T.; Nishimura, T.; Han,J.S.; Kobayashi, S. Chem. Letf., 1990, 2239.
$1
B(iPr)g , CF3S03H
80%
Olah, G,A,; Wu, A. Synthesis, 1991, 407.
OH
N a B h ,ether TFA ,25"C, 1 h
*
Nutaitis. C.F,; Patragnoni, R.; Goodkin,G.;Neighbour, B .; Obaza-Nutaitis, J. Org. Prep. Proceed. Int., 1991, 23,403. Nutaitis. C.F.; Bemardo, J.E. Synth. Cummun., 1990, 20,487.
o:H
5% SmI2, HMPA ethylene glycol
0'b 'O PC
RT,3h
oo
0&.' O PC
Hanessian.;Gkard, C.; Chiara. J.L. Tetrahedron Lett., 1992, 33, 573.
90%
212
Section 154
Compendium of Organic Synthetic Methods, Vo18
0
Barton.;Jang, D.O.; Jaszberenyi, J.Cs. Tetrahedron Lett., 1992, 33, 2311. PhH , TsOH hv (A = 254 nm)
0
&0
/
P
h Brq
a
Piva. 0. Tetrahedron Lett., 1992, 33, 2459.
m
o
75%
Ph
H
1. TsCI , NaH ,THF 2. NaBH4 , NiC12.6 H 2 0 MeOH
92%
J. Chem. Soc., ferkin Trans. I, 1992, 1897.
Wang, F.; Chiba, K.;
3 eq. [VCkdTHF)612 [ Z ~ Z C ~ ~ I
Ph&
Ph OH
CH2C12
*
0 Ph 0 4 " # P h
59%
using acetate as starting material led to 91% yield of ketone Inokuchi, T.; Kawafuchi, H.; Chem. Lett., 1992, 1895. Also via: Section 160 (Halides and Sulfonates).
SECTION 154: HYDRIDES FROM ALDEHYDES For the conversion RCHO
CHO
-+
0.05 q.~ ( S - B I N A Pc104 )
I)Ct-Bu Wu, X-M.; Funakoshi, K.; &ai&
4
R-Me, etc., see Section 64 (Alkyls from Aldehydes).
CH2C12,RT
t-Bu (>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
<'c
b
2.H20
SiMe3
Wu, G.;Cederbaum, F.E.; &&hjJ.
SiMe,
95%
Tetrahedron Letf., 1990, 31,493.
Ph
l.t-BuLi, -78°C pentane/ether
/
2. -78"C, l h
+
/
&Jh
+
I
88% 6% v. W.F.; Ovaska, T.V.Tetrahedron Lett., 1990, 31, 627.
-
,OH
PhMe2SM, THF 2h
PhMe2SiwOH
Ph
6%
-k
cat. C Y ~ P - P ~ [ - C H ~ = C H ~ ] ~(5.2 82% M u m h v . P r o c t e r , G . Tetrahedron Lett., 2990, 31, 1051.
1)
SiMezPh
248
Section 196
Compendium of Organic Synthetic Methods, Vo18
/ Br--C
Bu3SnH PhH , 8OoC *
9""
-
C3 C- SiMe,
0.5 [(PPh3)c~iH]6
Ph- CE C-Ph
5 H 2 0 , PhH , reflux 1.5 h
SiMe,
16%
tandem cyclizations Kilbum.J.D. Tetrahedron Len, 1990, 31, 2193.
*
Ph
Ph
w
91%
Daeuble, J.F.; McGettigan, C.; Strvker. J.M., Tetrahedron Lett., 1990, 31, 2397.
OTMS M< Me3Si-Si-CzC7( Mi Me Me
me351
FeC13 A
MqSiCl
CMezSi
Me
kc+Me 82%
Tetrahedron Lett.. 1990, 31, 5607.
Bu3SnHt THF (MeCNhMo(C0)y
n-C3H&: C- n-C3H7
(a-al1yl)Br
-
AnBu3
n-C3H7
n-C3H7
95%
Zhang, H.X.; GuiM. F,; Balavoine, G. .I. Org. Chem., 1990, 55, 1857. [PhMgBrlLnCI,]
I
C
Me Ph Me Wang, R-T.; Chou, F-L.; J.uo.F-T.J. Org. Chem., 1990, 55, 4846.
Hooc-,ph
68%
V o c 1 3 , PhCl , reflux 70 h ,proton sponge
Meier, I.K.; Schwartz. J, J. Org. Chem., 1990, 55, 5619.
n-C,H,,-CE C-H
Zn , 1,2-dibromoethane EtOH , 1 h
Aerrsens, M.H.P.J.; van der Heiden, R.; Heus, M.: 3421.
n-C6H13\
>90%
Synth. Cornmun., 1990, 20,
Alkenes from Alkynes
Section 196
X
F Zc-( Me
~ - C ~ H I
-
n-GHis R,Sn
F
C*
H Me
249
+
n-C7Hl$flrC--(
Bu3SnLi. THF ,78"C X=Br, R=Bu (50 MqSnCuBrLi ,THF X = OTs, R=Me (100 Marshall. J.A.; Wang,X J. Org. Chem., 1990, 55, 6246.
50) 0)
SnR,
Me
67% 75%
1.2 ea. DibaJ
(8020 Z:E) Kuchin, A.V.; Markova, S.A.; Gorobets, E.V.: Tolstikov, G.A. Izv. Akad. Nauk. SSSR,1990, 39, 1151 (Engl., p. 1034). 1. Bu3SnSiMe3, THF cat. Pd(PPh3)4 , 60°C
Ph-
'%Me3
Ph-
CEC-H 2. HI , Bu4NI , PhMe 0°C Mori. M,; Watanabe, N.; Kaneta, N.;Shibasaki, M. Chem. Lett., 1991, 1615.
(>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<
,t-BuCHO M%N
t-Bu
OH
81%
NMq
m a c . i i c h i . M.; Hayashi. A.; Minami, T. J. Org. Chetn., 1991, 56, 4091.
Br
H-ci c--/
1 . B u ~ SR~T,, 12 h 2. BuMgBr , THF ,O°C
3. PhCHO , 1 h O°C + RT
OH
b
P h L C3 c.
B a n g , L.J.: HmgJL - Huang, Z-11. Tetrahedron Lett., 1991, 32, 6579.
91%
OH
Ph-Cg-U , THF
ph
OH
Ph
e-99 4) 96% Chini, M.; U F , ;Favero. L.; Macchia, F. Tetrahedron Lett., 1991, 32, 6617.
Ph-CE C-(
OBn Me
Cp+3Ciz, BuLi THF , -78°C
BR*OEtz, PhCHO* THF , overnight 0°C -) RT
P
h
c'..cq Me
(86
Ph
+
Ph?
Me
Ph OH
14)
80%
(3: 1 antixyn)
Ito, H.; Nakamura, T.; 3kguchi. T,; Hanzawa, Y. Tetrahedron Leu., 1992, 33, 3769.
Section 304
Alkyne - Amide
8%
279
cat. OsO4, O°C , 3 0 h
Ph- Ci C
d
*
Ph-CEC<
OH OH
91%
(53% ee)
OMe
N
Jeong, K-S.; Sjo, P.; &arp&s.,J€&
Tetrahedron Lett., 1992, 33, 3833.
.
1. Dihal THF -20°C. 1 h
c
2 . 4 . NH4CI
Nussbaumer. P.; Stiitz, A. Tetrahedron Lett., 1992.33. 7507.
SECTION 303: ALKYNE
- ALDEHYDE
NO ADDITIONAL EXAMPLES
SECTION 304: ALKYNE
- AMIDE n
1. h 4 e q S . N
78%
0
U
PhC0,Me
2 BuLi , THF , -78°C + 0°C
2.
ON Me
NEt3. CHzClz
0 "
RT
@ ,
o
Ph-CEC-S-N
n0
w
7%
LeClercq, M.; Briennc, M.J. Tetrahedron Lett., 1990, 31, 3875. CO ,THF , S O T 5% Pd(0Ac)z
n - C 7 H p C I c+ Me0,CO
lcool
Mandai.; Ryoden, K.; Kawada,M.;
0
Er
Ts
66%
Tetrahedron Lett., 1991, 32, 7683.
- AMINE
mBr
1. Triton-B , MeOH 40°C
Ph
'C.* c~
K~C03.6h
NHTs
SECTION 305: ALKYNE
w
2. 110°C 3. MeNHBr
Frey, H.; b p p . G, Synthesis, 1990, 931
MexCx-H Ph
NHBn
88%
280
Compendium of Organic Synthetic Methods, Vol8
dC1 , PdCW'Ph3)2 Br
Section 306
CI
Ph- CE C- H
Ph-Cr C-Cr C-NEt,
CUI, PPh3, N E t 3 , 14 h* reflux 2. EgNLi , ether, 14 h , RT
15%
Synthesis, 1990, 125.
Loffler, A.;
Bu.
1.
Bu.
Bu-Cd2-H , PdC12(PPh3)2
N
CUI, NEt3, RT
PhA C1
Lin. S-Y; Sheng, H-Y.; Huang, Y-Z. Synthesis, 1990, 235.
N
PhLC:
C- Bu
60%
BuNH2,3% CuBr MeCN ,20"C, 5 h
* -&NZiiH
92%
Gen. R.; Polizzi, C.; Lardicci, L. Tetrahedron Lett., 1991, 32. 7471.
;-
- ESTER
SECTION 306: ALKYNE
0
Pd(OAc)z, N E t 3 ,EtOH
Ph- Cg C- I- Ph OTs 614.
OSiMe3 F=( , Sn(OTf)z Me
20%
80%
H,; Stang, P.J. J. Chem. SOC.,Chem. Cotnmun., 1990,
Xitamura. T,; Mihara, I.; -chi.
BU- Cr C- CHO
Ph- CE C- CO,Et
b
CO , RT
P.8 SEt
Me
*
OSiMe3 EtSJQCS C- Bu Me
€I
67%
(93:7 syn:anti; 91% ee)
CH2C12, -78°C Mukaiyama, T.; Furuya, M,; Ohsubo, A.; Kobayashi, S. Chem. Lett., 1991, 989.
H- Ci C
JCOZH
1. t-BuOK 2. Bu-CS-Br ,THF-MeCN /
Pd(P(o-tolyl)3 ,25"C 48 h
Bu'
Bouyssi, D.; Gore, J.; Balme, G. Tetrahedron Lett., 1992, 33, 281 1.
C.'
c** 41%
Alkyne - Ether
Section 307
SECTION 307: ALKYNE
c1- c: c- c1
28 1
- ETHER, EPOXIDE, THIOETHER 2 E t S H , 2 KH , THF 0°C + RT , 20 h
EtS- Cr C- SEt
87% Riera, A.; CabrC, F.; Moyano, A.; Perich, M.A.; Santamarfa, J. Tetrahedron Lett., 1990, 31, 2169.
0'" 0-crc-I
Sorensen, H.;
c"
! 0'"
BICH~CH~B Zn~ , THF , Me3SiC1 CsHllBr
1. n-BuLi 2.ZnBr2 3. H20
OMe
n - C 6 7 13
C 8.1
C-Me
56%
Tetrahedron Len.,1990, 31, 7597.
C: C- %Me3
Courtemanche, G.;
"'0-CEC-n-CSHII
CuCN , THF
*
QCM:-siMe3 OMe
80%
- Tetrahedron Lett., 1991, 32, 5317. 4% Mn (salen) derivative NaOCl , CH2C12, RT
pH 11.3,5 h
n-C6H!3
-
C
'5
+
0 Me
(2:l trans:cis) trans (93% ee , SR) cis (58% ee) Lee, N.H.; lacobsen.E.N.Tetrahedron Lett., 1991, 32, 6533. Me3Si-CK-SiMe3 S n C 4 , -20°C
AcO" OAc Tsukiyama, T.; hobe. M. Tetrahedron Lett., 1992, 33, 7911.
AcO"'
85%
282
Compendium of Organic Synthetic Methods, Vol8
0
0
(iBuzTeCHzCCSiMe3) Br I LiTMP ,THF
PhCHO
Section 308
p
t
-78°C 4RT
h
q
q.-
76%
c.
SiMe,
(82: 18 cistrans)
Mukai, C.; Uchiyama, M.;
Hanaoka.M..Chem. SOC., Chem. Commun., 1992,
SECTION 308: ALKYNE
n-C,HqCE C-H
1014.
- HALIDE
FkF ,CuI ,NEt3 I
F
c
Pd(PPh3)2C12 RT 3 70°C
n-C,H,-CX
F
69%
Yang, Z-Y.; Burton. D.J. Tetrahedron Lett., 1990, 31, 1369.
93% Wagner, A.; Heitz, M.P.; Mioskowsk i. C,Tetrahedron Letl., 1990, 31, 3141.
W CO,H F
Ph
1. Br2 , CC4 ,reflux 2. NaHC03, acetone reflux
d"CPh
Ph
3. PhCSCH , PPh3 Pd(OAc)z, B u N H ~
F
49%overdl
Eddarir, S.; Francesch, C.; Mestdagh, H.; Rolando, C. Tetrahedron Lett., 1990, 31.4449.
Ph- C3 C-H
Me3SiOOSiMe3 ZnI2 , THF
Ph-CZ C-I
90%
Casarini, A.; Dembecb.; Reginato, G.; Ricci.;Seconi, G. Teirahedron Lett., 1991, 32, 2165.
0
I ( o A ~ ) ~Me3SiCII2CaC-H ,CHzCl2 BF3.0Et2 , MgSO4, -20°C lh
c &
I
C=C-H
80%
.. Ochlar.; Ito, T.; Takaoka, Y.; Masaki, Y. J. Am. Chem. Soc., 1991, 113, 1319.
Alkyne - Ketone
Section 309
SECTION 309: ALKYNE
0
283
- KETONE
n-C3H7-CeH,RT
/b 1% [RhCI(PMqE] L acetone
0 C Z C J 86%
4
Tefrahedron Left., 1990, 31, 7063.
Nikishin, (3.1.; &N&YJ
6
Me-CH=C=CHSnPh, THF , -4O"C, 30 min
6..C
M~
86%
Haruta. J,; Nishi, K.; Matsuda, S.; Akai, S.; Tamura, Y.; Kita. Y . J . Org. Chetn., 1990, 55, 4853. 1. t-BuOK, t-BUOH 2. HCS-IPh BF4 RT,2h
0
0
..
Ito, T.; Takaoka, Y.;Masaki, Y.; Kunishima, M.; Tani, S.; Nagao, Y.J. Chem. Soc., Chem. Comrnun., 1990, 118.
;
0 PPh,
Ph
Br
1 . 1 2 , K 2 C 0 3 , MeOH 2.PhCHO,2K2C03
MeOH ,60°C
-
CrC-Ph
64%
Iman, M.; Bouyssou, P.: Chenauli. J. Synthesis, 1990. 631.
.
silica gel, -20°C , 1 h RT ovemighl
H-CEC
silica gel catalyzed Eschenmoser reaction
Abad.;Agullb, C.; Am6, M.; CuRat, A.C.; ZaragozA, R.J. SynLen, 0
NHiPr
1.5 eq. LiTMP , 0°C , 1 h 2 . 3 q.TMS-CI , -70°C 2h
1991, 787.
0
Ph- Cr C 4
Ph Me 3. AcOH ,AcONa ,pH 4;. Me Bartioli. G.; Cimarelli, C.; Palmieri. G. Terrahedron Lett., 1991, 32, 7091.
80%
284
Compendium of Organic Synthetic Methods, Vo18
0 E
t-BuMeZSiO,,,
EtzN
Q
Section 31 1
~ O c ~ OSiMcyc-Bu ~ ~ .
PhH, RT
t-BuMqSiO,,,
Yoshino, T.; Okamoto, S.; &&& J. Urg. Chem., Z99Z. 56, 3205.
Ciattini, P.G.; Morera, E.;
n-CgH17.Cf C-H
Tetrahedron Lert., 1991, 32, 6449. 1. HB(0iPrh 2. BF3*OEtzICHKIz Ph , reflux, 8 h
Ph rr-C8H17-CiC
Ph
Ph
Fujishima, H.; Takada, E.; Hara, S.; SuzdaA ‘ Chem. Lett., 1992, 695.
SECTION 310: ALKYNE
-
NITRILE
NO ADDITIONAL EXAMPLES
SECTION 311: ALKYNE
( c1
- ALKENE
1.6 €IC=CMgCI , THF 0.065 NaI , 0.15 CuCl 15 h c
2 . 2 BuLi ,THF , -78°C 3.THF, -78°C .6 h ClJ=Ll
5%
Gleiter. R,; Merger, R. Tetrahedron Letr., 1990. 31,1845.
OH
*
CUI, NEt3 ,60”C OH 85% Mieaani. GL;Chevalier, C.; Grass, F.; Allmang, G.; Morel, D. Terrahedron Lett., 1990, 31, 5161.
285
Alkyne - Alkene
Section 31 1
OTHP &
Pd(PPh3)4, LiCl CUI,NHEtz ,THF
n - c 6 H 1 y T ciC-Bu OC0,Me
)eB"
n-C6H13
*
Me
60%
RT , 3 0 min
q.*
cL. OTHP
Mandai, T.; Nakata, T.; Murayama, H.; Yamaoki, H.; Ogawa, M.; Kawada, M.; Tsuii. J, TefrahedronLeft.,1990. 31, 7179.
Me C.B.
c=c<
Me
Bu3SnH, AIBN , PhH 80°C
Me
Br
C.
Me
J. Org. Chem., 1990, 55, 2983.
Ph2MeSi- Cr C-H
RhCI(PPh3hYRT PhMe , 3 0 h
Ph2MeSi c
%
CE C- SiMePh2
94% Ohshita, J.; Furumori, K.; Matsuguchi, A.; j&&am&. J. Org. Chem., 1990, 55, 3271.
Me
PhOCHZCK-H
,,C02Me 4%Pd(OAc)z, TDMPP
zc-i H
~
Me
PhOJ Trost.;Kottirsch. G. J. Am. Chem. Soc., 1990, 112, 2816.
6'.c
32%
Balova, LA.; Remizova, I..; Favorskaya, LA. Zhur. Org. Khim., 1990, 26, 729.
pmdta = pentamethyldiethylenetriamine Dfxien, S.; Clinet, J-C.; Duaach.; PCrichon, J. J. Chenz. Soc., Chem. Commun., 1991, 549.
286
Section 3 11
Compendium of Organic Synthetic Methods, Vol8
Arcadi, A,; Cacchi. S,; Del Mastro, M.; Marinelli, F. SynLett, Z99Z, 409. 1 . SiamyhBH 2, B u - C d - L i
Bu-C' C-H
BuXC:C-Bu
w
60%
Neeishi. E,; Yoshida, T.; Abramovitch, A.; Lew, G.; Williams, R.M. Tetrahedron, 1991, 47, 343.
1. Br+3.
0
/
, Py-HF
Ph- CEC - H
.c
Ph
b
2. P h C S H , Pd(0Ac)z PPh3, NEt3 , 3 h reacts with alkenes to give dienes reflux
Ph
wc 83%
F
E:Z)
(92:8
Eddarir, S.; Mesldagh, H.; Rolando, C. Tetrahedron Lett., 1991, 32, 69.
bOTf
TfO
2.4 eq. Me3Si-CS-H 4% PdC12(PPh3)2
15% CuI THF-iPr2NH
Suffert.;Briickner, R. Tetrahedron Lett., 1991. 32, 1453. 1. 12, THF
M CSiMe3 ~C-H
n-C6H 13
Me&
2. Bu-CS-SnMe3 (MeCN)PdC12
n-C H
+
74%
Stracker, E.C.; Zweifel. G,Tetrahedron Lett., 1991, 32, 3329. n-CsHlI-CS-H, piperidine PdC12(PhCN)z , 3 0 min
n-C5H1 1-
Y
c1
SiMe3 CiC-H
l3%
Bu-CZC
n-C5H11 t
Alami, M.; Linstrumelle, C. Tetrahedron Lett., 1991, 32, 6109.
= i
q.\
C.
93%
n-C5H1 1
287
Alkyne - Alkene
Section 3 1 1
Bouyssi, D.; Balme, G.; Gore, J. Tetrahedron Lett., 1991, 32, 6541. Br ,Aliquat-336
H-Cg C<
H
30%aq. NaOH ,CuCl CHKlz, 20°C. 24 h J. Org. Chem., 1992, 57, 2188.
Grushin, V.V.;
60%
Pd(OAc)z, Pph3,CuI
OTBS n-C5H1 I
87%
1)
(8
Torii. S.; Okumoto, H.; Kotani, T.; Nakayasu, S.; Ozaki, H. Tetrahedron Lett., 1992, 33, 3503.
Br- CE C-(
0~~
DMF ,20°C
SnBu3,
*
OEt
\c:c-<
OEt PdC12(MeCN)z, 1h Beaudet, I.; Parrain, J-L.; Q&ard. J -P, Tetrahedron Lett., 1992, 33, 3641.
OEt
H- C: C- C02Me
1 . LiBr-AcOH , MeCN , reflux 2.Ph-Cg-H , PdCIz(PPh&
80%
* Me@C. q..
c k dPh
u; Huang, X.;Ma, S. Tetrahedron Lett., 1992, 33, 2535. 1. PhBr , PdC12.2 PPh3
H- Cr !\ SEt
PPh3, CuBr ,NEt3 reflux
2. Zn , EtOH ,reflux 3.N a H 2 NH3 (Iiq)
4. H 2 0
7
w
Ph\=/
c!'
85%
H 54% overall
Fossatelli, M.; van der Kerk, A.C.T.H.M.; Vasilevsky, S.F.; Jha&mJ. Tetrahedron Lett., 1992, 33. 4229.
288
Section 313
Compendium of Organic Synthetic Methods, Vol8
REVIEWS :
"Molecular Design, Chemical Synthesis, and Biological Action of Enediynes"
Nicolaou.;Smith, A.L. Accts. Chem. Res., 1992, 24, 497.
SECTION 312: CARBOXYLIC ACID
- CARBOXYLIC ACID
Muzart.; Ajjou, A.N. Synth. Cornmun., 1991, 21, 575. montmorillonite , 3 0 T
Choudarv. B.M.; Valli, V.L.K.; Durga Prasad, A. Synth. Cornmun., 1991, 21, 2007.
SECTION 313: CARBOXYLIC ACID
0
- ALCOHOL, THIOL
1. HCN , iPr20
CHO (S)-oxynitrilase 2.aq.HCI 70% (98% ee)
Effenbereer. F,; Hiirsch, B.; Ftirster, S.; Ziegler, T. Tetrahedron Lett., 1990, 31, 1249.
'<
0
E'O'bEt 0
1. LiNTMSz , -78°C 2.2.2 q.PhCHO ,-78°C 3.aq.NaOH
--
HO c-(Ph
OH
+
OH H02Cpph
Me
Me
4, H ~ O +
1.2) 97%
(98.8
Longmire, C.F.; Evans. S.A. Jr. .I. Chem. SOC., Chem. Commun., 1990, 922.
Bu
5 eq. immobilized Rhodococcus sp. 24 h
Bu X C O * H
62% Klempier, N.; de Raadt, A.; Faber, K.; Griengl, H. Tetrahedron Lett., 1991, 32, 341.
Acid - Alcohol
Section 3 13
1. PhCHO , Zn TMSCl , PhH 2. KOH , MeOH
289
+
OH HOOC,&H Ph (44% ee , R)
51%
Basavaiah. D,; Bharathi, T.K. Tetrahedron Lett., 1991, 32, 3417.
Me
1
Me*
COzH
B(0iPr)Z
NEt3 ,CHzClz
HO Me +CO,H
+
Me
95%
(99: 1 synmti)
Wang,2.; Meng, X-J.; Kabalka, G.W. Tetrahedron Lett., 1991, 32, 5677.
9
BSLDH ,NADH H+ , 2.8 d
COzH
OH T C O Z H
66%
(99% ee) BSLDH = Bacillus stearothermophilus lactate dehydrogenase Casv. G,; Lee, T.V.; Lovell, H. Tetrahedron Lett., 1992, 33, 817. 1. [NaOWKCVNaOCI1 , MeOH *. KI , j n n m
c
OH
/h/ OH
+ 24% mandelic acid
Ph C02H 57%
Guthrie.;Cossar, J.; h..L Can. .I. Chem., 1991. 69, 1904.
P h Y O 0-
5% R u ~ ( C O D ) ~ ( O ~ C C F ~ ) ~ 2 dppb , 10 eq. HCOOH OH + Ph dC02H 10 eq. NEt3 reflux, dioxane
Shimizu. I.; Tekawa, M.; Maruyama, Y . ; Yamamoto, A. Chew Lett., 1992, 1365.
SECTION 314: CARBOXYLIC ACID
- ALDEHYDE
NO ADDITIONAL EXAMPLES
80%
290
Compendium of Organic Synthew Methods, Vol8
SECTION 315: CARBOXYLIC ACID
- AMIDE
r
1. Ni(COD)(TMEDA)z THF ,reflux + CbzHN 2. H3O+
CbzHN
Section 315
0
CO,H
+
(Co2H
CbzHN
(9
1) 60%
1:l mixture when Ni(COD)(bipy)~was used Castailo, A.M.;
Tetrahedron Lett., 1990, 31, 4783. F
N A N F A N a F
CbzHN
w
Py , CH2C12,4 h
CbzHN
89% Bertho, J-N.; Loffet, A.; Pinel, C . ; Reuther, F.; Sennyey, G. Tetrahedron Lett., 1991, 32, 1303.
HOOC-NHCHO 1. Pd(0Ac)z , P(o-Tol)~ c ~-Bu H-N" N- C0,Me 100°C, NET3 , DMF .-
Ad
0
Meoel Q ,24h
OMe
2. NaBH4 ;H3O'
3.3N HCI 66% 4. A c ~ OHCOOH , J
BocHN
7 Co2H
1.3 eq. LDA
P
w
BocHN
23. H3O+
Co2H
48%
De Nicola, A.; Einhorn. J.; m e . J -L, Tetrahedron Lett., 1992, 33, 6461.
C02H M e 4 NH,
Ac2O Hz0, ))I)))
*
Me--(co2H NHAc
Veera Reddy, A.; Ravindranath. B, Synth. Commun., 1992, 22, 257.
96%
Acid - Amine
Section 3 16
SECTION 316: CARBOXYLIC ACID
29 1
- AMINE
1. NaN(TMS)2
NH2 3. 1N aq. HCI ,RT 4.ZnIaq. HCI ,AcOH 5. aq. LiOH ,THF 6. ion exchange
0 2
H02C83%
(>99%ee, R)
ODDolzer. W,; Tamura, 0. Tetrahedron Lett., 1990, 31, 991.
M ~ ANx ph Me
Ph
1. acryloyl chloride
2. NH3 C H K h 3. CICOZBn, NEt3
Nfi
I
*
HOOC
Y Me
NHyHCI
4. Hg(OzCCF3)z 5. NaBH4, MeCN 6. HCI, MeOH ,reflux
Amoroso, R.; Cardillo. G,; Tomasini, C. Tetrahedron Lett., 1990, 31, 6413. I. t-BuLi , THF , -75°C 2. C@
NHBoc
PhSimig, G.;
3.20% HCI ,reflux
8h
*
phTNHBOC 55%
Tetrahedron Lelt., 1991, 32, 1963, 1965. 0
Ph
Y
CO2Et 1.
F
Ph,r C02H
~ NH2 C vTEBA ~
K2CO3, MeCN , 80°C 2. KOH , M e O H , RT,2 h
Br
NH2
64%
Landini. D.; Penso. M.. I Org. . Chem., 1991, 56, 420.
Me-N3
t-Bu -(
N
1. LDA 2. BnBr 3. 6N HCI ,heat
4. Dowex 50W-X8
+
1
HOOC
olll
\
Ph
H2N BZ' 50% Juaristi. E.; Quintana, D.; Lamatsch, B.; Seebach. D,J. Org. Chem., 1991, 56, 2553. REVIEWS: "New Approaches to the Use of Amino Acids as Chiral Building Blocks in Organic Synthesis" Reetz. M.T,Angew. Chem. Int. Ed. Engl., 1991, 30, 1531.
292
Compendium of Organic Synthetic Methods, Vo18
Related Methods:
Section 319
Section 3 15 (Carboxylic Acid - Amide). Section 344 (Amide - Ester). Section 351 (Amine - Ester).
SECTION 317: CARBOXYLIC ACID
Phwco2Et
- ESTER
porcine liver acetone powder H20, pH 7.2, RT, 7 h
- PhyCOzEt
96%
C02H
COzEt
Ahmar, M.; Bloch.;Bortolussi, M. Synth. Commun., 1991, 21, 1071.
SECTION 318:
CARBOXYLIC ACID THIOETHER
OBOM SnBu3 Chan, P.C-M.;
- ETHER, EPOXIDE,
1. BuLi , THF , -78°C
2. co2 3. H+
*
9BOM e C 0 2 H (95%=) 99%
Tetrahedron Lett., 1990, 31, 1985.
0
NaSPh ,aq. iPrOH 0°C -+ RT
*
E C O O H 95%
Breitschuh, R.; m c h . D, Synthesis, 1992, 83.
SECTION 319: CARBOXYLIC ACID
- HALIDE, SULFONATE
1.3 eq. LDA
GMi
Welch. J.T.; Plummer, J.S.; Chou, T.S. J. Org. Chem., 1991, 56, 353. BIyNEtZPh, PhH RT,7h
-
Me
Narayana, C.; Reddy, N.K.; Kahalka. GW, Tetrahedron Lett., 1991, 32.6855.
87%
Acid - Ketone
Section 320
293
Starostin, E.K.; Mazurchik, A.A.; Ignatenko, A.V.; Nikishin. G.1, Synthesis, 1992, 917.
SECTION 320: CARBOXYLIC ACID
-
KETONE
1. AcCl, N-methylmorpholine
+
c
2. AICI3
67%
(>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.
1. P O 0S E M
-
cat. hydroquinone xylene ,reflux H O 2 . 0 ~ 0 4NMO , , aq. THF OH 60%overall SiMe$'h 3. mr, 15% ACOOH AcOH , NaOAc , RT , 1 h Koreeda. M,; Teng, K.; Murat, T.Terrahedron Lett.. 1990, 31, 5997.
* M~ M~
OH
1. (HMe2Si)flH ,NH3 2. [RhCl(ethene)]z, R-BMAP DCE ,30"C ,6.5 d
3.30% HzO2, KF ,K H C G MeOH , THF
M~ +OH OH
60%
(95/5 sydanti; 80%ee)
Tamao. L;Tohma, T.; Inui, N.; Nakayama, 0.;Iray,Tetrahedron Letr., 1990, 31, 7333.
c1
A*
Mo (NOj ;;fi
€I
51%
Ph
Lin, S-H.; Vong, W-J,; Cheng, C-Y.; Wang, S-L.; LiuJLS Terrahedron Lett., 1990, 31, 7645. 0 ~ 0 4 KjFe(CN),j ,
tBuOH, H20,RT K2CO3,24 h
Minato, M.; Yamamoto. K. ; Tsuji, J. J. Org. Chem., 1990, 55, 766.
$, 0
PhCHO , CrC12 THF ,LiI O"C,lh
Fujimura, 0.;Takai.;
Ph OH OH (9 8
+ OH OH 2)
J. Org. Chem.. 1990, 55, 1705.
95%
Section 323
Alcohol - Alcohol
1. catecholborane ,THF -lO°C, 5 h
2. aq. Na K tartrate, MeOH
*
*
297
82%
(101 syn:anti)
Evans. D.A,; Hoveyda, A.H. .I. Org. Chem., 1990, 55, 5190. 0
OH
3 eq. BuLi , 0°C ether-pentane
88%
* 6 ) OBuH
OH
u; AM-El-Aziz, AS.; Lough, A. J. Org. Chein., 1990, 55, 5305. OTBDMS 5% OsO4,25"C
BnO
Brio OTBDMS >H
2 eq. NMO
TBDMS-O HO
TBDMS-0
Brio
OTBDMS
+
C O , ~TBDMS-0
(9
w;Morikawa, Y.;
H O CozEt 96%
1)
J. Org. Chein., 1990, 55, 5429.
aq. Dowex-SOW
71%
reflux, 30 min
Ranu.; Chakraborty, R. Synth. Coinmun., 1990, 20, 1751. 0
OH
Ph
MeTi(OiPr)3, ether LiI , - 7 8 -+~ - 2 0 0 ~
Ph
Ph
Ukaji, Y.; Kanda, H.; Yamamoto, K.; m 0
PhKPh 0
OH OH
Me OH
4
Me
a
,Yb,RT.18h
THF , HMPA
.c
Ph
(99 . T. Chern. Lea., 1990, 597.
1)
OH P h m Hph-& Me +
Ph Me
Ph
OH
37%
46% (90% ee) Takaki, K.; Tanaka, S.; Beppu, F.; Tsubaki, Y.; Fuiiwara. Y,Chein. Left., 1990, 1427.
69%
298
Compendium of Organic Synthetic Methods, Vol8
Section 323
Pseudomonas sp. (BM 2)
OH
G e w , P.J.; P&c&&~ Commun., 1990, 204.
35% 3% Roberts, S.M.; Ryback, G.; Winders, J.A. J. Chem. Soc., Chem.
GOH
1. HzKO (500 psi), PhH [Rh(OAc)2]2 , iOO°C
Op(OEt),
*
2. LiAIH4, ether
72%
OH
Jackson. W.R.; Perlmutter, P.; Tasdelen, E.E. J. Chem. SOC.,Chem. Commun., 1990, 763.
Me- . M e Br Si-
1. Bu$nH, 1-BuOH AIBN , reflux
2.30%H 2 0 2 , THF K H C 0 3 , MeOH reflux Koreeda.; Hamann, L.G. J. Am. Chem. Soc., 1990, 112, 8175.
t-BuMezSiO
G'U""
___L
Me
f-BuMezSiO
(a) SmIz , THF , RT (b) Sml,, THFhexane , RT ( c ) SmI@-Bu , THF , RT
80%
9'"qo o?-B&e2Si0
Me OH
(a)
(b)
(C)
Me
0%
71% 35% 0%
41%
15%
Ilenishi. J,; Masuda, S.; Wakabayashi, S. Tetrahedron Lett., 1991, 32, 5097.
+
Ph
Ph
O s 0 4 , NMO 1 0 1 acetone:H20 +
*
75%
(24%ee , SS)
fk'
Pini, D.; Petri, A.; Nardi, A,; Rosini, C.;
PhxPh HO OH
.
Tetrahedron Lett., I991, 32, 5175.
Section 323
Alcohol - Alcohol
1. I-BuOK , THF -78°C
Ph
2. H202, K F KHC03
t
* 0
PhCHO , SnC12 Bu,NBr, DMI L, 25"C, 1 6 h
&OH
66% Tetrahedron Lett., 1991, 32, 6383.
Matsumoto, K.; Miura, K.; Qshima;
Me
299
M s P h
Ph
+
OH OH
DMI = dimethylimidazolidin-2-one
7)
(93
Masuvama. Y,;Nakata, J.: Kurusu, Y. .I. Chem. SOC., Perkin Trans. 1, 1991, 2598.
89%
1. Li" ,naphthalene ,THF 1 h , -78°C
Yus. I%;
2. iPrCHO , -78°C 3 RT * 3. H 2 0 Rambn, D.J. J. Chem. Soc., Chem. Commun., 1991, 398. Re2O7, H 2 0 2 , 1 6 h
n-C8H17-
/
90"C, dioxane
n-C H
l 7 - " y 0 ~
'"qH phqH L,
OH
62%
Wanvel. S; Klass, M.Rg.; Sojka, M. J. Chem. SOC., Chem. Contmun., 1991, 1578. 1 aq.acetone,25"C . 0 ~ NMO 0 ~ ~
ph\
2.Na2S205
Ph
+
* HO
HO HO
~ 0 ' 'Ph (16
Park, C.Y.; Kim, B.M.; Shamless. K.B. Tetrahedron Lett., 1991, 32, 1003. 1. Bu3SnH, AIBN PhMe
2. TBAF
1)
Ph 87%
-3
59% HO
HO
Hutchinson.J.H.; Daynard, T.S.; Gillard, J.W. Tetrahedron Lefr., 1991, 32, 573.
Section 323
Compendium of Organic Synthetic Methods, Vo18
300
PdC12(PhCN)2 , SnCl2 70 h
0
xq!
-
&OH , TIf F ,0°C
(82:18 syn:anti) Kurusu, Y. Chem. Lett., 1991, 879.
Takahara, J.P.; ;.Y-
N
,
BH3, ~ THF ~ aq. NaOH
~
(90
u, Mckee, S.P.; Sanders, W.M. Tetrahedron Lett., 1991, 32, 711. Ph2CuLi
0
L
-
7
Devine, P.N.;
RMgX ,R2CuLi
10)
86%
BxoH
Bn
similar results with
OH
86%
a:;+ 0::
Tetrahedron Letf., 1991, 32, 883.
C
1.0.1 M S d 2 , THF
CHO I-BuOH , -78°C + 2 5 T CHO 2. 10% Na2S203
(93
Chiara, J.L.; Cahti, W.;
Tetrahedron Letr., 1991, 32, 1125.
'
B(OiPr)* (98:2 E:Z)
Wang, Z.; Meng, X-J.; &&&a.
A
OH N E t 3 , CH2C12 28 h
+
81%
HO Me +OH
*" Me
72%
(97:3 syn:anli)
CHo
HMPA 2.10%aq. Na tartrate
Raw, AS.; & h s g ~ U . J. Org. Chem., 1991, 56, 830. *
7)
C.W. Tetrahedron Len., 1991, 32, 1945.
1.2 eq. VC13(THF)3 I .4 ZII , CH2Cl2
Park, J.;
75%
OH
Tetrahedron, 1992, 48, 2069.
82%
Alcohol - Alcohol
Section 323
Ph-
[Rh(COD)z]+ C1042. NaOH ,HzO
Matsumoto, Y.; HayuhJ, '
B
011 OH
1)
40% ee
U
2. H@z, NaOH
OH OH
*
OH OH
-
Bu
+ B u / Y Me
Me
3. TBAF
(24
When step 1 is 9-BBNITHF/-78"C-25"C
62%
44% ee
Tetrahedron Lett., 1991, 32, 3387.
1. catecholborane ,PPh3 1% [Rh(COD)C1]2
V
OH
OH (3
0SiMe2r-Bu Me
30 1
1)
(1
Bureess. K,; Cassidy, J.; Ohlmeyer, M.J. J. Org. Chem., 1991, 56, 1020.
9)
1. LDBB ,THF ,-78°C 2. Et3AI ,M e e T H F , -70°C 3. iPrCH0
*
+OH
52%
LDBB = 4,4-di-t-butyl biphenylide Mudryk, B.; Cohen. T. J. Org. Chem., 1991, 56, 5760.
0.2%C A N , H 2 0 , MeCN 25 min
+
Ph
1.2.2 eq. SmI2, THF HMPA
O16% H
80%
6
Baltork. I.M.; Zardaloo, F.S. Tetrahedron, 1991, 47, 9861.
N-;.
T
HO,,,
80%
a;H +M
I . Org. Chem.,1992, 57, 3132. Molander. G.A,; McKie, J.A. .
Me-
'.
3/SiPhzC1
-
.NEt3
OH 2.190"c 3. KF , 1 4 2 0 2
Me
(1
Sieburth. S.M,; Fensterbank, L. .1. Org. Chem., 1992, 57, 5279.
1)
71%
Compendium of Organic Synthetic Methods, Vol8
302
Section 323
1 . Li , BFpOEt2, naphthalene 2. iPrCHO
0
+OH
*
3.aq,HCI
76%
Rambn, D.J.; Yus.M. Tetrahedron. 1992, 48, 3585. 1% Os04 , K?Fe(CN)6, HzO
K2CO3, r-BuOH , RT
r.
OH
5% L N ~ O S i P h z l - B u
Oishi, T.;
83%
(41% ee , SS)
OSiPh2l-Bu
Tetrahedron Len., 1992, 33, 639.
OAICI, 2
Sarlori.
\
FeC13, MeN02, RT Sh
+
78%
OMe OMe OMe G; Maggi. R.; Bigi, F.; Arienti, A,; Casnati, G.Tetrahedron Lett., 1992. 33, 2207. O s 0 4 ,aq. MeCN , NMO
Ph
c
polymer-bound dihydroquinidine , 24 h
-;1-"
Ph
86%
OH
(82% ee , RR)
Lohrav. B.B.; Thomas, .-.;Chittxi, P.; Ahuja, J.; Dhal, P.K. Tetrahedron Len.. 1992. 3 1 . BnNEt3 B H 4 , Me3SiCI CHZC12 ,0°C
2. 10%K2C03 Baskaran, S.; Chidambaram, N.; Narasimhan, N.; 33, 6371.
c
rL
HO
HO
5453.
69%
Tetrahedron Lett., 1992,
(90% ee)
m,Tanaka. K.; Miyamoto, H. Tetrahedron Lett., 1992, 33, 4021.
Alcohol - Alcohol
Section 323
303
P h q Ph OH
quant.
(73% ee , RR)
Imada, Y.; Saito, T.; Kawakami, T.; Murahui. S-I. Tetrahedron Left., 1992, 33. 5081.
DHQD-IND , cat. OsO4
Ph/-7Nle DHQD-IND=
72% ee (1R.23
0
J, Am. Chem. Soc.. 1992, II4,7568.
Wang, L.;
Ph
K3Fe(CN)6, K2C02,O"C t-BuOH, H20
Ph
1 % oSo4 , K3Fe(CN)6 +
ph&Ph
DHQD2-PH AL
84%
OH
DHQD2-PHAL = 1,4-bis-(9-O-dihydroquinidinyl)3 +99% eel phthalazine - see J. Org. Chem., 1992, 57, 2768. Xu, D.; Crispino, G.A.; -J. Am. Chem. SOC., 1992, 114, 7570.
3% Ni(mac)2,02 DCE.MS4Am8h 100°C
HO
*OBz
OH
90%
(85: 15 1 ,2-diol:1,3-diol) nickel (11) Ni(rnac);! = bis-(3-methyl-2,4-pentanedionato) Mukaivama.; Irnagawa, K.; Yamada, T.; Takai, T. Chem. Lett., 1992, 231. Ru(acac)3 , tetraglyme P(n-Cd41713 H2 200"C, l-I3Po4,3 h
-c
oH
27%conversion 95% selectivity
Hara, Y.; Inagaki, H.; Nishimura, S.; Wada. K,Chem. 1Rlt.. 1992, 1983.
Compendium of Organic Synthetic Methods, Vo18
304
Section 323
Me3SiCI. NaI , Srn MeCN, 15 min
84% Ph s ! h OHMe Akane, N.; Kanagawa, Y.;Nishiyama, Y.; Ishii. Y, Chem. Lett., 1992, 2431.
b \
.RT
I . 0 3 , CH2C12 , O°C 2. Hz Pd-C , EtOH
OMe
b''OH
*
&OH
+-
+OH
+OH
(3
1)
41%
Culshaw, A.J. Synktt, 1992, 214.
;-
E t f i l , PhH-hexane [PhBrL? sec-BuLi;Al]
Meb
0
H
0°C --t
RT
OH M e A O H
+
Ph Me+OH
Ph
OH
(20
1)
55%
Ahn. K.H; Kim, J.S.; Jin, C.S.; Kang, D.H.; Han, D.S.; Shin, Y.S.; Kim. D.H. SynLeft, 1992, 306.
0
Ph
#
N a B b ,EtOH , RT
N.OMe 0 Me Sibi. M.P. ; Sharma, R. SynLett, 1992, 497.
P hOH V O H
92%
REVIEWS:
"Recent Advances in the Asymmetric Dihydroxylation of Akenes" Lohrav. B.B. Tetrahedron Asymmetry, 1992, 3, 1317. "New Aspects of Stereoselective Syntheses of 1,3-Polyols" Dishi. T,; mats. T. Synthesis, 1990, 635. Also via:
SECTION 324:
Section 327 (Alcohol - Ester); Section 357 (Ester - Ester).
ALCOHOL, THIOL
- ALDEHYDE
Siedlecka, R.; Skarzewski. J.; Mfochowski, J. Tetrahedron k t t . , 1990, 31, 2177.
305
Alcohol - Aldehyde
Section 324
OMe
A
1. PPh3, TMSOTf 2. BuLi , THF, -78°C
3. PhCHO , TMSOTf = H r c H o 4. KOH ,MeOH 77% 5. H+ Kim.;Kim, Y.C. Tefrahedron Lett., 1990, 31, 2901.
0 Me,SiO
THF,-78OC
Li
Kane., Kim, D.H.; Lee, J.H.; Rim,J.G.; Yoon, Y.B.; Kim, K. .I. Org. Chem., 1990, 55, 5555.
1 . MeTi(OiPr)3 ,ether 1 h (>99:1 dr)
2. HCUHzO - ether
Me p Ph
w
H CHO
70% Tetrahedron Lett., 1991, 32, 29 19.
Ukaji, Y.; Yamamoto, K.; Kukui, M.; l&&&yLL 1 . BuzBOTf , iPr2NEt
\)IN A 0
CH2C12,O"C 2.EtfiAICI.CH2C12 hexanes ,-78°C
0
OH 0
V
N
(add enolate to Et2AEIl
'
Me
OH 0
O V I
-
+
N
'
Me
3. iPrCHO
5)
(95
0 O
u
63%
Walker, M.A.; Heathcock. C.H,J. Org. Chem., 1991, 56, 5747.
ph?-tph
TolO2S' N.sNS02Tol , -780c 1.
n-C5H1 ICHO
LC K - H
2.5 h
2. t-BuMe2SiC1, imidazole 3.03
Corev. E.J.; Jones, G.B. Tetrahedron Lett., 1991, 32, 5713.
OSiMe2t-Bu n-~5~11< CHO 98%
306
Section 325
Compendium of Organic Synthetic Methods, Vol8
1. Dibal , PhMe , 0°C 2. satd. NH4CI 3. 1.6N H2S04, 18 h
Ph
69%
Ph
4.9N HCI , 15 h SynLett, 1991, 479.
Hayashi, M.; Yoshiga, T.;
MABR , -78OC
** 0
87%
40 min
Ph-0SiMe2i-Bu I-BU
(98% ee)
I-Bu
MABR = B r q o h i o + B r I-BU Mel-Bu
Maruoka, K.; Ooi, T.; Nagahara, S.;
Tetrahedron, 1991, 47, 6983.
Section 330 (Alcohol - Ketone).
Related Methods:
SECTION 325: ALCOHOL, THIOL
- AMIDE
iPrCHO ,THF LHMDS ,- 100°C
96%
Ph
Ph
(>99% de 3S.4R)
Oiima.;Pei, Y. Tetrahedron Lett., 1990, 31, 977. 1. EbNIO, ,MeOH -78°C 2. cyclopentadiene
HO Ph wNHoH
OH
"5':
H o
Ph
3.Na/Hg,MeOH NaH2PO4
77%
Miller, A.; Procter, G. Tetrahedron Lett., 1990, 31, 1043.
0 N Boc
1. set-BuLi ,TMEDA ether 2. PhCHO
OH m
P
h
N Boc 39% Bealr.;Lee, W.K.J. Org. Cheni., 1990, 55, 2578.
+
J-0 0
~~~
Ph 37%
Section 325
Alcohol - Amide
307
%MeoKPh -78'C
0
PMP
OMe,
HO
1. LDA , THF
2. MeCHO f-78°C -+ RT
0
Ph
PMP
80%
PMP = p-rnethoxyphenyl
Durst.; Sharma, M.K.; Gahe.;Lee, F.L. J. Org. Chem., 1990, 55, 5525. HOCHzCHzNH2, e'
PhC02Me
*
B z H N ~ o H 73%
; Ueda, A.Can. J. Chem., 1990,
Arai, K.; Tamura, S.; Masumizu, T.; Kawai, K.; 68, 903.
3; C1eNHB 1.2.2eq. BuLi 2. 10°C 3. H f l
82%
\ /
Smith.;hitchard, G.J. Angew. Chem. Int. Ed. Engl., 1990, 29, 282. I . BuLi , T H F , -105°C 2. PhCHO
0
0
*
E(2N\Ph
OH
65%
Hiiro, T.; Mogami, T.; Eambe. N,; Fujiwara, S.; Sonoda. N. Synth. Cornmun., 1990, 20, 703.
E:-
OH AI(H6) , aq. THF , ))))))
0 Bn
/
e 0. N - 0 B n
Luzzio.; OHara, L.C. Synth. 0 P
0
Commun., 1990, 20, 3223.
BuMnCl
v NMe,
h
70%
Me
Bu,, 0 Ph@NM+ Me
+-
(>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 (<2:98
OSiMe,
OSiMe, Ph
f-BuQCf..
2. 1. LDA PhCHO
*
3.TMSCl
Z:E)
t y f
Ph
%.% (60
40)
Curtis, A.D.M.; Y&&gJ. Tetrahedron Lett., 1991, 32, 1507 W h i t i a Tetrahedron Lett., 1991, 32, 1503.
j-0-
+q+y
(56:44 in THF at -78°C ; 0100 in THF at 22°C
Wei.;Bakthavatchalam, R. Tetrahedron Lett., 1991, 32, 1535.
/
M:gE;;p2 t
EtOH ,85 min
+
49%
OEt
CHO 5%
. . Shlmlzu.; Watanabe, Y . ;Orita, H.; Hayakawa, T.; T~IUULL Tetrahedron Lett., 1991, 32, '
2053.
Alcohol - Ester
Section 327
323
Sartori, G,; Casnati, G.; Bigi, F.; Baraldi, D. Tetrahedron Lett., 1991, 32, 2153. 1. R*2BBr, NEt3
Br,
C02t-BU
Bu$nH, PhH AIBN,reflux
OH
ph+C02r-B~
-78OC
2. PhCHO CHEl2
OH
*- .
ph+,C02t-B~
Br
74%
86% (98:2 anti:syn) 96% ee
h y . F. J; Cho, S. Tetrahedron Lett., 1991, 32, 2857.
OH
bakers yeast
50°C, + MVK 30 min
&C02Et
Me
:
+
&CO,Et
OH
h C O 2 E t
Me
Me
3) 94% (97 Nakamura.; Kawai, Y.; Ohno, A. Tetrahedron Lett., 1991, 32, 2927. Nakamura.; Kondo, S.; Kawai, Y.; Ohno, A. Terrahedron Leu., 1991, 32, 7075.
OH EtO2C+
1. Soclz 2. LiBr ,acetone, 50°C
CO Et
OH
E ~ ( - J , cCO ~ /2Et
3.2.5 Zn , H 2 0 (cat.)50"C, 2 h
OH
70%
Ga0.y.; Zepp, C.M. Tetrahedron Lett., 1991, 32, 3155. OD HO
-,*.
OAc OEt
Ti(OiPrhOAc,1 h CHC13
HO&OEt
6H
0
OAC OEt i-
HO+OEt OH -2) 95%
(>98
Raifeld. Y.E,; Nikitenko, A.A.; Arshava, B.M.Tetrahedron Asymnzetry, 1991, 2, 1083.
0
H2 (100 atrn), 25OC 0.5 [R~C12Ph]2
(R)-BINAP , 4 0 h Kitamura, M.; Tokunaga, M.; Ohkuma, T.;
.
OH &COW (99% ee , R)
97%
Tetrahedron Lett., 1991, 32, 4163.
Compendium of Organic Synthetic Methods, Vol 8
324
Section 327
OH COzEt CO,Et Me
2 Sm12,THF
de&-JMe 79% (31:l % dr)
Molander.; Kenny, C. J. Org. Chem.. 1991, 56, 1439. 0
0
bakers yeast, 16 h "fermentation
N3
N3
N3
19%(70% ee)
49% (70%ee)
Hudlickv.; Tsunoda, T.; Gadamasetli, K.G.; Murry, J.A.; Keck, G.E. J. Org. Chem., 1991, 56, 3619.
C02Me
RuCI~(COD),, Wt3 PhMe , 140°C, MeOH
-CO,Me
HO
90%
(97%ee) Taber. D.F.; Silverberg, L.J. Tetrahedron Lett., 1991, 32, 4221.
0 Bn2N/OE1
1. mCPBA 2. H2 , Pd(OH)2
*
Me400a
Me
90%
OH
(>95%ee) Reetz.; Lauterbach, E.H. Tetrahedron Lett., 1991, 32,4481.
ph4,/c02u
NaBH4, MnC12
Me Fujii, H.;
w;
i
OH phJyco*Et
+
Me (90
Terrahedron Lett., 1991, 32, 6141.
OH ph+co2Et
Me 10)
90%
Alcohol - Ester
Section 327
325
wmg. 2.;M e w X-J.; Kabalka, G.W. Tetrahedron Lett., 1991, 32, 4619. Me02CA0
BuzBOTf , iPrzNEt -78°C .+ 25°C
Me
(8
55%
92)
QhL; Wrobel, Z.; Rubenstein, S.M. Tetrahedron Lett., 1991, 32,4647. 1. Sn[Co(C0)414 , 1-120
Ph-
Br
pgooH+
Ca(OH)2, CO (65 bar) f-BuOH
Ph
2. H30'
CC13CF3. CISiMe3 e' (Pt cafhode/C anode)
d C F 2 C O 2 M e 89%
Shone.; Kise, N.; Oka, H. Tetrahedron Lett., 1991, 32, 6567.
+*'
0, N
SH
'04 0
COzMe
NaOMe ,MeOH , 4 8 h
2. Ph(C=O)SH , Tic14
w
LC02Me Me
HS
(39% ee) Shono.,Matsumura, Y.; Fujita, T. Tetrahedron Lett., 1991, 32, 6723.
MeC02Me
1. Dibal , -78"C, BFyOEt2 2. Me Me-OEt
C02H
OH
DMF , EWOTs
1.
Ph
C02H
67% Tetrahedron tett., 1991, 32, 4703.
Monflier, E.; Pellegrini, S.; Mortreux.,
ACHO
Ph%zoH
OSiMe3
*
Kivooka. S,; Shirouchi, M.J. Org. Chem., 1992. 57, 1.
67 %
% OH
Me Me
C02Et
Me
70%
Compendium of Organic Synthetic Methods, Vol 8
326
0 menthyl'
s';
1.
..
Me02C&
0
.
. 4 eq. LDA THF -78°C
2.ZnCl2 , Dibal ,THF , -78OC * 3. Ni(R)
Me02C
PDC , I-Bu00H
CH$12,8 h
0
L-
-OH 0
0°C -i 25°C
Chidambaram, N.; Bhat, S.;
82%
J. Org. Chem., 1992, 57, 5013.
0
PhCHO , -4OOC CHzClz
Me ;
.- 7 8 T
OSiMq
M~~~~~
20% BHzTHF
>*Q
H02C
2. TBAF ,THF
-
Me NHTs
-S
Me
E
OH 0 t
P h v S E t Me
-k
13)
(87 (80% ee)
Pannee, E.R.; Hong, Y.; Tempkin, 0.;
OBz
18%
OH 0 PhO
OH Me
Me 70% Olivier, E.; Ouimet, N. Tetrahedron Lett., 1992, 33,457.
PhCHo
81%
(97%ee)
SolladiB. G; Almatio, A. Tetrahedron Lett., 1992, 33, 2477.
-3
Section 327
89%
(94%e)
Tetrahedron Lett., 1992, 33, 1729.
4 eq. Smlz ,THF-HMPA
-78°C + 23°C
I
(35:l)
Enholm. E.L; Jiang, S. Tetrahedron Lett., 1992, 33, 6069, 313,
PhCHO
Ph
BrCH2C02Et , Cp2TiClz-Zn b
THF , RT , 5 min Dine.;Zhao, G . J. Chem. SOC.,Chem. Commun., 1992, 941.
OH
C02Et
90%
327
Alcohol - Ester
Section 327
€!m&&gA;Leijonmarck, H. Tetrahedron Lett., 1992, 33, 3025. iPrCH2CHO ,Tic14
OSiMe2t-Bu 75%
(59:41) Tetrahedron Lett., 1992, 33,
Vasconcellos, M.L.; Desmaele, D.; Costa, P.R.R.; dUg&!J 4921.
~
PhCHO
~
~
~
MeN02, -78°C
"
'
,
phQ0zEt p-NOzPhS02
92%
(90%ee , R)
"
Kivooka. S,; Kaneko, Y.; Kume, K. Tetrahedron Lett., 1992, 33, 4927.
Tetrahedron Lett., 1992, 33, 1465,
Gu, J-H.; Terada, M.; Mikami, K.;
In - ICHZCOzEt THF - pentane cinchonine
PhCHo Johar, P.S.; Araki, S.; m
Y
.
-
OH Phk C 0 z E t
63%
71% ee , R)
. Chem. Soc., Perkin Trans. I, 1992, 711.
RuCI2-n H 2 0 , PhH , RT t-BuOOH, 4 h
0 phAO/\/OH
Murahashi. S.; Oda, Y.; Naota, T. Chem. Lett., 1992, 2237.
79%
328
Compendium of Organic Synthetic Methods, Vol8
cp
2% Ph2 I
h
r
-
B
~
w
@
0
p- Fe'
Bach, T.; Fox, D.N.A.;
p
,20b
+oSiMeZf-Bu OMe
PhCHO
Section 328
COzMe
77%
ReazJIL J. Chem Soc., Chem. Commun., Z992, 1634.
'
OH
C02t-BU Zn ,MegSiCl
0 Br
Br Escudier, J-M.; Baltas, M.;
98%
Tetrahedron Lett., 1992, 33, 1439. Ti(OAc)3, aq. AcOH RT,3h
*
OH
50%
Ferraz. H.M.C,; Ribeiro, C.M.R. Synrh. Commun., 1992, 22, 399, Section 313 (Alcohol - Carboxylic Acid).
Also via:
SECTION 328:
ALCOHOL, THIOL THIOETHER
- ETHER, EPOXIDE,
Bewersdorf, M. Tetrahedron Lett., 1990, 3I, 67.
n-C3H70H, 0.2% DDQ 90 min
IranDoor.;Baltork, I.M. Tetrahedron Lett., 1990, 31, 735.
IranDoor.;Baltork, I.M. Synth. Commun., 2990, 20, 2789.
diastereomers (85:15)
OH 92%
Alcohol - Ether
Section 328
329
55%
9)
(9 1
Alexakis.;Hanriizi, J.; Jachiet, D.; Normant, J-F. Tefrahedron Lett., 1990, 31, 1271.
0+
C02Et t - B u P h ' S i O d
1. TBAF ,THF m 2. Pd(Ph3)4 , THF 11.5 h
r c o 2 y
CozB
OH
OH
8)
(92
82%
Suzuki, T.; Sato, 0.;Hirama. M,Tetrahedron Lea.,1990, 31, 4747.
17)
(1
Angle.;Amaiz, D.O. .I. Org. Cherrt., 1990, 55, 3708.
B F3
0 khavarren.
+
Ho&,,,(H'
0
N- NMe,
NMe,
aJ. Org. Chem., 1990, 55, 4255.
( 5 :1
Molander. G.A,; Harring, L.S. .I. Org. Chem., 1990, 55, 6171.
trans:cis)
71%
67%
330
Compendium of Organic Synthetic Methods, Vol8
OSiMe,
Section 328
1. TMSOTf
M
e
0
4
OMe
2. "MSOTMS , DMAP
Lee.; Cregg, C. S y d e r f , 1990, 317.
V-PILC ,PhH , r-BuOOH
-OH
OH
RT
96%
V-PILC = vanadium-pillared montmorillonitecatalyst
Uuudary. B.M.; Valli, V.L.K.; Prasad, A.D. J. Chem. SOC., Chem. Commun., 1990, 721.
y ' "OH
Dillwed-montmorillonite.35 h *
T
Ti(OiPr)4, (+)-DIPT '
O
H 86%
Choudarv.;Valli, V.L.K.; Prasad, A.D. J.
(94%ee)
Chem. SOC., Chem. Commun., 1990, 1186.
LTA, PhH, RT. 2 h
BySn OH Yamamoto.; Irk,S.; Arase, T.; Kohmoto, S.; Yamada, K. J. Chem. Soc., Chem. Commun., 1990, 1492.
OMe
1. BuLi 2.BughBr
A SnBu3 3. Tic4
n-C,H,,
OMe n-C7H&
~-C~H~SCHO
n-C7Hl OH
+
(99
OMe n-C7H1& n-C7H1 OH 1)
84%
(39:61 in 95% yield with BF3.OEt~ratherthan Tic14
Yamada. J.; Abe, H.; Yamamoto, Y. J. Am. Chem. Soc., 1990, 112, 6118. n-C6H 13
f - 3
oyo Ph
1. MqBBr ,-78°C
2. BH3mTHF
b
r_(n-C6H
HO
(14
OBn
13 +
r(n-c6H'3 BnO
OH
1)
83%
Guindon, Y.; Girard, Y.; Berlhiaume, S.; Gorys, V.; Lemieux, R.; Yoakim, C. Can. J. Chem, 1990, 68, 897.
Alcohol - Ether
Section 328
33 1
20% Co(modp)z, i M H
Ph
t-BuOOH,MS4A.02 50°C, 30 min (-0
0 ' 0
modp =
73%
99% trans selective
0
Inoki, S.; Muka ivama. T,Chem. Lett., 1990, 67.
Q-p 0
Pons, J-M.;
.
Y
TiC14, Mg ,THF
71%
OH
Tetrahedron, 1990, 46, 513. ZrCb-LiAlH4, ether, RT
30 min quant. Shaozu, W.; Tianhui, R.; Yulan, Z. Bull. SOC. Chim. Belg., 1991, 100, 357. Shaozu, W.; Yin, C.; Yulan, Z. Bull. Soc. Chim. Belg., 1991, 100,421 (with CpTiCIyLiAlHq), 1. S d z , THF ,HMPA RT, 10min 2. aq. NH4CI
=-
qyH 55%
Shibuya, K.; Nagaoka, H.; Yamada, Y. .I. Chem. Soc., Chem. Commun., 1991, 1545
2)
(1
72%
Shimada, S.; Saigo, K.; Makamura, H.; Hagegawa, M. Chem. Lett., 1991, 1149. MqSi,
PhCHO
S,
SiMq
TBAF, THF, RT, 20 h
*
Phy OH SMe 98%
Hosomi. A,; Ogata, K.; Ohkuma, M.; Hojo, M. SynLett, 1991, 557.
332
Compendium of Organic Synthetic Methods, Vo18
Section 328
o r -- p*8'' PbSnBu3 1. BuLi , TMEDA , THF -90°C
Ph
OH
2. PhCHO
Ph
Lohse, P.; Loner, H.; Acklin. P.; Slernfeld, F.;
f\l
87%
Tetrahedron Lett., 1991, 32, 615.
1. TMSOTf ,CHzClz
BHpSMeZ, -78°C
O-OH
0 0 P h A P h 2. NaHCO3
P h A P h
95%
Hunter. R.; Bartels, B.; Michael, J.P. Tetrahedron Len., 1991, 32, 1095.
MeC02v +Hov 02CMe
0
porcine pancreatic lipase
pH 6.5 , -5"C, 26 h
0
54% conversion (90%ee)
Grandjean, D.; Pale, P.; Chuche, J. Tetrahedron Lett., 1991, 32, 3043. (OAC
fOH
l.Zn(BH& , DME
OBz
OBZ Panu. B.C.; Basu, M.K. Tetrahedron Lett., 1991, 32, 3243. ZrCh-LiAIH4, ether
ph401 0
;
30°C. 1 2 h
PhJ0>
93% OH
i-
P h 7 7%
OH
Tianhui, R.; Ning, C.; Yulan, Z. Org. Prep. Proceed. Int., 1991, 23, 427.
Me02cwC
'yo
02Me I . MelBBr , 20°C
c-C6H 1 1
2.M&u(CN)Liz -30°C
Me02Cw
C02Me Me02cHC02Me
JMeOH
+
c-C6H 1 1
(17
1)
83%
Guidon.;Simoneau, B.; Yoakim, C.; Gorys, V.; Lemieux, R.; Ogilvie, W. Tetrahedron Letl., 1991, 32, 5453.
Alcohol - Ether
Section 328
dOH
0
333
1.2.2eq. BuLi ,DME ,0°C 2.2.0 eq. B(OMe)3 , 0°C
SiMe$-Bu
ph&oH
3. PhBr , Pd(PPh&, reflux H 2 0 , DME
0
SiMe2t-Bu 68%
Cristofoli, W.A.; b v . B.A. Tetrahedron k i t . , 1991, 32, 5881. CH2C12, MS 4 A ,0°C Id
(80
20)
50%
Mikami. K.; Terada, M.; Sawa, E.; Nakai. T, Tetrahedron Lett., 1991, 32, 6571. mCPBA ,aq. NaHCO3
OH
25"C, 7 h
OH 83% Fringuelli. F.; Germani, R.; Pizzo, F.; Santinelli, F.; Savelli, G. J. Org. Chern., 1992, 57, 1198.
-
SnCI4, MeOH , -30°C 30 min
H Ph+OH Me0
88%
(95% ee)
Moberg.
6; Rakos, L.; Tottie, L. Tetrahedron t e t t . , 1992, 33, 2191. hv (350 nm) PhH,4h
Me
0
c
90%
Ph
Sumathi, T.; Balasubramanian. K.K,Tetrahedron Lett., 1992, 33, 2213.
OH
t - B ~ 0 0 HCHC13 , MS 4 A ,45"C, 72 h
*
+OH
73% Antonioletti, R.; Bonadies, F.; Locati, L.; Screttri. A, Tetrahedron Len., 1992, 33, 3205.
Compendium of Organic Synthetic Methods, Vol8
334
SiMe,
'02,
Section 328
"'Oo Me3Si_
Ti(OiPr)4
*
70%
Adam. W,; Richter, M. Tetrahedron Leu., 1992, 33, 3461.
Re207
OH
%OH
Kennedv.,Tang, S. Tetrahedron Lett., 1992, 33, 3729.
N
0
N
1. LHDMS , THF 2. BnBr 3. LiEt3BH , THFC
0
ePh
H
O
RT
59%
T Ph SPh
92%
Orena, M.; Porzi, G.; Sandri. S . Tetrahedron Lett., 1992, 33, 3797.
Me3Si
0
BuLi ,ether
CHO
-78°C
i)H
HO (29
a
Urabe, H.; Matsuka, T.; &Q&
Bu
Me3Si 71)
75%
Tetrahedron Lett., 1992, 33, 4179.
mMe
Hq
1 . 3 eq. Re207 3.3 eq. 2,6-lutidine
OH 2. NaOOH
Me
62%
H
(5.8:l trans:cis) Tang, S.; K e n n e w Tetrahedron Lett., 1992, 33, 5299, 5303. AIBr3,Oz , PhH
+
6OoC, 18 h
*
%H 85%
EQC
& OH
Antonioletti, R.; Bonadies, F.; Lattanzi, A.; Monteagudo, E.S.; Scettri, A. Tetrahedron Lett., 1992, 33, 5433.
Alcohol - Ether
Section 328
335
OH
OH
0
(9
91)
82%
Li, K.; Hammn, L.G.; Dreeda. M, Tetrahedron Lett, 1992, 33, 6569.
1. SmIz
80% Curran. D.P.; Totleben, M.J. J. Am. Chem. Soc., 1992, 114, 6050.
J
Bu
0
NaBH4-CaC12
THF , 0°C (85
85%
15)
Fujii, H.; Oshima. K.; Utimoto. K, Chem. Lett., 1992, 967.
1. Ph4
N
0 S H$&iZCH$'h
Ph
H @ b MeOH , RT, 5 h Ph 2. aq. HCI ,CHzClz 3. DMSO , PhCH(Me)NIIZ 50°C.30 min Karikomi, M.; Narabu, S.; Yoshida, M.; M C h e m . Lett., 1992, 1655.
80%
REVIEWS: "Rearrangementof Epoxyalcoholsand Related Compounds" Org. Prep. Proceed. Int., 1990, 22, 547. "Transformation of P-Hydmxyalkylselenides to Aldehydes and Ketones. A Review"
Krief.;Laboureur, J.L.; Dumont, W.; Labar, D. Bull. SOC.Chim. Fr., 2990,
127, 681.
"StereocontrolledManipulations of ChromatographicallyResolved Pyranosides"
Mash,&& SynLett, 1991,
529.
Compendium of Organic Synthetic Methods, Vol8
336
- HALIDE, SULFONATE
SECTION 329: ALCOHOL, THIOL
Phv
BuzSnHz ,0°C
+
* phJBu OH
0
Bu
0
(0
with Bu$nHZ/DNB
Section 329
100) 82% 10) 75%
(90
DNB = p-dinitrobenzene (radical inhibitor)
Shlbata.;Nakamura, K.;Baba, A.; Marsuda, H. Tetrahedron Lett., 1990, 31, 6381.
Br PhCHO
(
c1 RT
*
OH P
hc1 h + p
85%
h
13% L
C
l
Ph 2%
+
Y h d e r . P A ; Grissom, J.W.; Hoffmann, U.;M a R. Terrahedron Lett., 1990, 31, 6605. C02&
LDA ,PhCHO F F3CL C02Et -9OOC. 2 h
F,C-p
OH 80%
also undergoes conjugate addition and alkylation reactions Qian, C-P.; Nakai. T, Tetrahedron Lett., 1990, 31, 7043. ByN' H 2 F i , 120°C
KHFz , 8 h
+
Ph
h + F OH
Ph
(39
.. Landml.; as^& Tetrahedron Lett., 1990, 31, 7209.
obtain a 1:l mixture at 2S'C
(7
Alvarez, E.; Nuaez. M.T.; Martin, V.S. J. Org. Chem., 1990, 55, 3429.
Imai.;Mishida, S . J. Org. Cheni., 1990, 55, 4849.
)7
HO
F
61)
1)
74%
89%
Alcohol - Halide
Section 329
6
1. MeOH ,NaI ,NaOH
0°C Me 2. NaOCl , 2 T , 1 h 3. 100/oaq.sodium thiosulfate
m.K.L; Failing, S.N. J. Org. Chem., 1990, 55, 5287 CuO.HBF4,
331
6" OH
I
80%
-&
I2
60%
MeCN , H20
I
Barluenpa.;Roddguez, M.A.; C m p o s , P.J. J. Chem. Snc., Perkin Trans. I, 1990, 2807.
-
1. EtMaBr 2. Ti(GPr),
0 *Ph
b
3. aq. H+
xoH 83%
Ph
Sosnovskii, G.M.; Astapovich, I.V. Zhur. Org. Khim., 1990, 26, 911 (Engl., p. 781).
4
&10~-NaAS03
aq.MeCN,RT 2h
Ohta, H.; Sakata, Y.; Takeuchi, T.; IshijJ
> 4io
25
70%
; Giordano, C. Synthesis, 1990, 327.
B u ~ P H Fneat, ~, 4 h
n-C 1 ZH
26% OH
53% I Chem. Lett., 1990, 733.
4 eq. C13CCOOH , HMPT RT,8h
CHO
Ferraccioli, R.;
+
l0O0C
*
KF
n-C 12H25
F +
n-C I 2H2& 7)
(93
OH 94%
Seto, H.; Qian, Z . ; Yoshioka. H.; Uchibori, Y.; Umeno, M. Chem. Lett., 1991, 1185.
0
ph%o~s
Et2AlCl , CH2C12 -55OC
+ -5°C , 2 F
c1
Cl
Ph+OMs OH
(92 Gao, L.; Saitoh, H.; Feng, F.; Murai. A, Chem. Lett., 1991, 1787.
+
Ph+OMs OH 8)
quant.
338
Compendium of Organic Synthetic Methods, Vol8
Section 329
LizCuBrd, THF , 4 h c "
. . Clacclo.; Heller, E.; Talbot, A. SynLett, 1991, 248.
3Me
CH212, Sm ,THF
t
n-C6H13
Br
p* M~
n-C6H13
93%
diols available from chloromethyl ethers Imamoto. T, ;Harajima, T.; Takiyama, N.; Takeyama, T.; Kamiya. Y.; Yoshizawa, T. SOC., Perkin Trans. I, 1991, 3127. bakers yeast, EtOH , sucrose (ketone added to yeast slurry)
*
Ph
Ph
Lcl 84%
(44% ee) Tetrahedron. 1991, 47,
LiI , AcOH , THF
RT ,20 min
Baiwa. J.S,; Anderson, R.C. Tetrahedron Lett., 1991, 32, 3020.
Ph
6 q.HMDS , DMF , CHF3 e- , Pt electrodes
A,Ph
[CHFdpymlidinonelDM; Bu~NX]
Ph+
CF3 OH Ph
84%
Shone.; Ishifune, M.; Okada, T.; Kashimura, S. J. Org. Chem., 1991, 56,2.
c)'
1. Me3SiCF3 , THF
TBAF
Krishnamurti, R.;Bellew, D.R.;
2.TBAF,THF
J. Org. Chem, 1991, 56,984.
OH
BrCF2CH=CH2,Zn
Ph-CHo Yang, Z-Y.;
THF,O+25"C
Chem.
OH
Noran. P.J.S,; de Carvalho, M.; Okamoto, M.T.; 2073.
0
I
*
J. Org. Chem., 1991, 56, 1037.
A g2 Ph
67%
Alcohol - Halide
Section 329
1. I Z ~ ( C N ) C U ( C H ~ ) & ~ I I THF , -60°C -+ -25°C
PhCHO
c
2. I2 , -70°C + RT
Achyutha Rao, S.;
339
L, 59%
Ph
J. Org. Chem., 1991, 56,4593.
J -Psi Connet-Delpon, D.; Lequeux, T. J. Org. Chem., 1991, 56, 5800.
Abouabdellah, A.; -6.
MgI2, PhMe -60°C
* &OH OH . . Bonml.;Righi, G.; Sotgiu, G. J. Org. Chem., 1991, 56, 6206. "OH
-ae
(Bu3Sn)2, PhH
hv (sunlamp)
BH2CbSMe2, -60°C
*
O
OH
66%
OH
Rawal. V.H.; Iwasa, S. Tetrahedron Lett., 1992, 33, 4687.
H Ph
85%
'k
OH
Ph
OH
(>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 <5 min
c
0 OSiMe, Phu p h 90%
Hollis, T.K.;Robinson, N.P.; Bosnich. B. Tetrahedron Lett., 1992, 33, 6423.
b
OSiM%
cat. Mn (salen) derivative PhIO ,MeCN ,25OC 70 min
&,OH
+
&osiMe3
(2.6
(30% ee)
Reddy, D.R.;
J. Chem. SOC., Chem. Commun., 1992, 172.
1)
70%
348
-
Compendium of Organic Synthetic Methods, Vol8
Section 331
35% H z q , 1.6% PCWP
CHCI3 ,H2S04, reflux 24 h
OH
aq. Dowex-50, reflux
0
Ph
Ph+Me Me OH Chakraborty, R.; Das, AX. ; R a n u . S y n r h . Commun., 1992, 22, 1523. 1.
*;
A0
EtCN
ph
N.
Tl
83%
67%
(93% ee)
BB,,
-78°C. 14 h 2. aq. H+ Corev. F.J.; Cywin,C.L.; Roper, T.D. Tetrahedron Lett., 2992, 33, 6907.
REVIEWS : "Uses of the Fries Rearrangement for the Preparation of Hydroxyarylketones"
klixLhA Org. Prep. Proceed. lnf., 1992, 24, 392.
"Selective Oxidation of a$-Unsaturated Ketones at the a-Position" Demir. AS,; Jeganathan, A. Synthesis, 2992, 235.
SECTION 331: ALCOHOL, THIOL BrZnCHzCEN
PhCHo
MqSiCI , THF reflux, 30 min
- NITRILE OSiMe, Phl\/C=N
8646
Palorno.;Aizpurua, J.M.; L6pe2, M.C.;Aurrekoetxea, N. Tetrahedron Lett., 2990, 31, 2205.
Matsubura, S . ; Onishi. H.; U t i m o u Tefrahedroti Lett., 1990, 31, 6209.
Alcohol - Nitrile
Section 33 1
349
''9 n
N-H
2% H - N , + f $
PhCHO
HCN , PhMe , -20°C 8h
Tanaka, K.; Mori, A.; -.I.
0°C , 18 h
CN
97%
(91% ee)
*
pdoSiMe3 CN
95%
(78% ee, R) Chern. SOC., Chern. Comrnun., 1990, 1364.
Hayashi, M.; Matsuda, T.; -.I.
PhCHO
PhR
Org. Chem., 1990, 55, 181. Me3SiCN. Ti(OiPr)4 (+)-DIFT, CH2C12
PhCHO
OH
H
0
PhCHgN , e - , -4OOC DMF-H?O, 80 mi%
HO&CN Ph 75%
+
CN ph& ph 8%
Torii. &; Kawafuchi, H.: Inokuchi, T. Bull. Chern. SOC. .Ipn., 1990, 63, 2430. Me3SiCN - CaO , 60°C heptane
&OAc
X
~
A + GC O
CN
0
OSiMe, 4)
(96
Sugita, K.; Ohta, A.; Onaka.;
A 75%
Chern. Left., 1990, 481.
QauhdL Bull Chem. SOC.Jpn.. 1991, 64, 3143. TMSCN ,CH2Cl2 cat. TMSOTf , -78OC
H
N=C OBn
Molander.;H a , J.P. Jr. J. Am. Chem. Soc.,
3 (7:l dr)
1991, 113, 3608.
OBn
50%
C
350
Section 33 1
Compendium of Organic Synthetic Methods, Vol8
Me3SiCNI CH2C12
PhCHO
@:r~
20% Ti(OiPr)4 -30°C 44h
1"
N-OH
p h i o SCi N Me3
90%
(67% ee , R)
Hayashi, M.; Miyamoto, Y.; Inoue, T.; Qggni. N, J. Chem. Soc., Chem. Commun., 1991, 1752.
, Ti(0liPr)4 , RT
O C H O
l-
Me0
87%
@:
Me0
0
Mori, A.; I n o u e . C h e m . Lett., 1991, 145. Mori, A.; Kinoshita, K.; Osaka, M.; Inoue.Chern. Lett., 1990, 1171. Me3SiCN. CHzClz
phwCHo
10% EtN(iPr)2,O0C
c
Ph4
OSiMe3 C N
*%
Kobayashi, S.; Tsuchiya, Y.; l g h W y m a . T, Chem. Lett., 1991, 537, 541. Me3SiCN , Yb(CN)3 , THF
0°C. 1.5 h
oo:re3 93%
Chem. Lett., 1991, 1447.
Matsubara, S.; Takai, T.; HCN
PhCHO
To% w
Me3AI
-78"C, 102 h (41%, 61% e ,R) -78°C , 7 2 h (87% ,3696 ee ,R)
Bn
C02Me
N<
Mori, A.; Ohno, 11.; Nitta, H.; Tanaka, K.;
Me3SiJ
CN
SynLetr, 1991, 567.
PhCHO , KF 3 min .-
microwaves (440 W)
P h F C N OSiMe3 62%
Latouche, R.; Texier-Boullet.,lbm&nJ, ' Tetrahedron Lett., 1991, 32, 1179.
35 1
Alcohol - Nitrile
Section 33I
Me0
1. LDA , THF , -70°C
OH
36%
CN
BhawaJ, B.M.; Khanapure, S.P.; Zhang, H.; U J. Org. Chem., 1991, 56, 2846. 2 eq. C12CeCHzCN, THF -78°C + RT , 4 0 min
Liu.; Al-Said, N.H.
T
Ir
C
N quant.
Tetrahedron Lett., 1991, 32, 5473.
LiC104, KCN MeCN ,70°C 8h
OH H-LCN
C
+
HIITOH n-C6H 13
n-C6H13
(98.2
1.8)
95%
Chini, M.; Crotti. P.; Favero, L.; Macchia, F. Tetrahedron Left., 1991, 32, 4775.
+
KCN ,znI2, TMS-CN *
Brunet. E; Batra, M.S.; Aguilar, F.J.; -0.
PhCHO
(>95:5 syn:anti) J.L.G. Tetrahedron Lett., 1991. 32, 5423.
BrZnCHzCN ,THF -13'C. 16 h cat
nf'A
p h Y C N OH
76%
OH (93% ee , S ) Me h i . & ; Hirose, Y.; Sakata, S. Tetrahedron Asymmetry, 1992, 3, 677.
reflux , 4 h -11.
-
OH d
D.; Koenig, T.M. Tetrahedron Lelt,, i992, 33, 3281.
C
N
74%
352
Compendium of Organic Synthetic Methods, Vol8
0;;
3.5 eq. LiCN , THF
*
reflux, 4 h
Section 332
"%
a c c i o . J.A.; Stanescu, C.; Bontemps, J. Tetrahedron Lett., 1992, 33, 1431.
oo @:
0'"
TMSCN ,CH2C12,2O0C
80%
18 h
"
Ti(OiPr14
OSiMe3
OH
I
N. SynLett, 1992, 663.
Hayashi, M.; Tamura, M.; @mi.
- ALKENE
SECTION 332: ALCOHOL, THIOL
4
1. CH3CHO
-78°C , 1h
2. NaOH ,H202
65% (90%ee)
OH
'I'
Brown. H.C,; Randad, R.S. Tetrahedron Lett., 1990, 31,455.
SPh
PhCHO ,Me2AICI OH Sph CH2Cl2 , -23°Cw P h~ O T ~
OTBS
20 h
Tanino, K.; Nakamura, T.; Kuwaiima
6 0
B
*#
6
OH SPh
+ p h + ~ ~ ~ ~
Me
Me
(94
6)
G H
Tetrahedron Lett., 1990, 31,2145.
1. Os04, NMO aq. 1-BuOH , RT 24 h
Ph. Ph- pJ
S
2. KOH , DMSO 50°C
Harmat, N.J.S.;W a r r e d Tetrahedron Lett., 1990, 31, 2743. [iPrMgCl , CpzTiClz] ether, Bu3SnC1
Bu
THF,reflux 6h
*
Lautens.;Huboux, A.H. Tetrahedron Lett., 1990, 31, 3105.
75%
Bu
86%
353
Alcohol - Alkene
Section 332
montmorillonite clay
clay catalyzed C l a i m reanangement
53%
Lett., 1990, 31, 3241.
SiMe3
Me3Si
2 e S i M e 3
2.2 TiC14, -78°C
BnO
+
B
n
y
O
/v
OH OSiPh,
CH2C12
88% (2,3 antikyn = 33/1) Shimazaki, M.; Morimoto, M.; Suzuki. K. Tetrahedron Lett.. 1990, 31, 3335. ZdAg-graphite THF , RT , 10 min
*
4 90%
Fiirstner. A, TetrahedronLett.. 1990, 31, 3735. SmI2, THF , HMPA
Me
t-BuOH, 0°C
*
X
Me
H
55%
Shim. SC,; Hwang, J-T.: B n p . H-Y,; Chang, M.H. Tetrahedron Lett., 1990, 31, 4765.
TsO 0
T e , NaBH4
*;: H __
5H 1 1
DMF
91 % Discordia, R.P.; Murphy, C.K.;Dittmer. D.C. TetrahedronLeu., 1990, 31, 5603.
SnBu3 OBn
1. SnC14 , -78°C , 5 min
2. PhCHO , -78°C. h 1* h; ' -
McNeill, A.H.; Thomas. EJ, Tetrahedron Lett., 1990, 31, 6239.
90%
354
Compendium of Organic Synthetic Methods, Vo18
Section 332
1. NBS , CCI, , K2C03 2. KO2, 18-crown-6
4 3
OH
458
Williams, G.M.Terruhedron Len., 1990, 31, 7509. Bnrnble. M.A.; Edmonds, M.K.; 1. PhMe, MS 4A (C6HI 1 0 ) M e 2 S i A B o.f0 o COziPr 2t iPr 2. H a , KHC03, MeOH
CHO
t-BuMe2SiOJ,
t - B u M e 2 S i O G
OH
THP ,55"C
67%
Boush. W.R,; Grover, P.T.; Lin, X. TelrahedronLetr., 1990, 31, 7563. Boush. W.R,; Grover, P.T. Terrahedron Len.,1990, 31, 7567. 1. BBr3 , CH2Cl2
-78°C + 25'C
KSiMe,
2.30%~~0~ 97% 3N NaOH ,reflux Hirai, A.; Suzuki, H.; Sonoda. N., Murai, S . J. Org. Chem,, 1990, 55, 1409.
w;
SiMe3
73 \,,at
HO
1. KH , I 2 , THF
65°C
2. TBAF , THF , 6 5 T
-0 74%
HO
tandem anionic oxy-Cope*allylsilane cyclization Jisheng, L.; GalIardo, T.; J. Org. Chem., 1990, 5.5,5426. 1, iPrCHO
Park, J.; Bdersen. S.F. J. Org. Chem., 1990, 55, 5924.
3 -
0
PhI , 10% Pd(OAc)?, BudNCl 3 HC02Li , 3 EtN(kr);! ,LiCl * DMF ,50°C, 1 d
Ph(79:21
Larock. RC,;Leung, W-Y. J. Org. Chem, 1990, 55, 6244.
' E:Z)
OH 78%
Alcohol - Alkene
Section 332
355
NEt3, CHC13 ,reflux 84% 3.1M HCI ; 1M NaOH Hosomi.; Kohra, S.; Ogata, K.; Yanagi, T.; Tominaga, Y. J. Org. Chem., 1990, 55, 2415.
,RT
Ph-Br
-CHO
Zn , DMF
4
87%
Ph
(75:15 erythro:threo)
Shono.;Ishifune, M.; Kashimura, S. Chem. Len.. 1990, 449. MeZAICI , CH2C12 /X"C
MABR , CH2C12, -78°C t
('
1)
(1
32)
65%
85%
Maruoka, K.; Ooi, T.; Yamamoto. H. J. Am. Chem. SOC.,1990, 112, 9011
SiMe3
0
C \\
SiMe,
E13Al , CH2C12 RT
Dost. B.M; Urabe, H. J. Am. Chem. SOC.,1990, 112, 4982.
OJl cu
1. ICH2ZnI 2. n-C5Hl lCHO
Knochei., Rao, S.A. J. Am. Chem. SOC., 1990,
86% 112, 6146.
356
Section 332
Compendium of Organic Synthetic Methods, Vo18
H
TiC14, -78°C
O
-"OQ
Bu3Sn
I,
+
(77:23 EZ)
1111
26)
(74
quant.
Yoshitake, M.; Yamamoto.; Kohmoto, S.; Yamada, K. J. Chem. SOC.,Perkin Trans, I,
1990, 1226.
-78T
-+
RT
-- d
+ OH
(22
1)
17%
Tanaka, T.; Inoue, T.; Kamei, K.; Murakami, K.; Jwata. C, J. Chem. SOC., Chem. Commun., 1990, 906. Bu3SnH1 AIBN , PhH
OH
HQ
54%
22%
Keck.;Tafesh, A.M. SynLert, 1990, 257. LDA ,t-BuOK
c
Q
88%
0 0 O"C,lh OH Mordini, A.; Ben Rayana, E.; Margot, C.; Schlosser. M.Tetrahedron, 1990, 46, 2401. 1. T i C 4 , O'C, 3.5 h 2. SiOz
Abouabdellah, A.; Auk* C.; Begue, J-P.;Bonnet-Delpon, D.; Guilhem, J. J. Chem. Soc., Perkin Trans. I, 1991, 1391.
Sarandeses, L.A.; Mouriilo, A.;
w. J -I,J. Chem. SOC.,Chem. Commun., 1991, 818.
Alcohol - Alkene
Section 332
BujSnH , AIBN PhH , reflux
357
SiMe3
Me3Si *
46%
syringe pump addition over 8 h
OH
(55:45
OH
EE:ZE)
Clive. D.L.J,; Cole, D.C. J. Chem. Soc., Perkin Trans. I, 1991, 3263. c-C~HIlCHO BF3'0E12
Bu3Sn
OMOM
L
Me
,
OH OH : c - q H , ,+ M e M c - C 6 H
,,
MOM
OMOM 5)
(95
74%
Marshall.; Welmaker, G.S.; Gung, B.W. J. Am. Chem. SOC.,1991, 113, 647. Marshall.;Luke, G.P. J. Org. Chem., 1991, 56, 484. 1. PhClIO , BF3eOEt2, -78°C
M°Cp(Co)2 2. Me3N-0, CH2Clz, 23°C
OH
APh
Lin, S-H.; Yang, Y-J.; Liu, R-S. J. Chem. SO~., Chem. Commun.. 1991, 1004.
6.
1. n-C6H 13MgBr. ether
CuBr.SMe2, -70°C
2.H20
c
Barber, C.; Bury, P.; Kociehski. P.; O'Shea, M. J. Chem. Soc., Chem. Commun., 1991, 1595.
Yf
OH Me
1. Co(dmgH)zPy
2. hv (sunlamp)
Me 76%
Harrowven, D.C.; Pattenden. G , Tetrahedron Lett., 1991, 32, 243.
>
CE
2 eq. Riecke Zn ~ ~ e O f W 0
30 min
60% ( 9 5 5 cktrans) Chou, W-N.; Clark, D.L.; White. J.B, Tetrahedron Left., 1991, 32, 299.
358
Compendium of Organic Synthetic Methods, Vo18
Ph
d
Section 332
10%Bu4NRe04 5 q.TsOH*H20
40%
CH2Cl2,RT Ph Narasaka, K.; Kusama, H.; Hayashi, Y . Chem. Lett., 1991, 1413. 1. Me2CuLi 2. LiAlH4, THF 3. KH ,THF
*
OH e n - C 5 H l l Me
Ito, T.; Yamakawa, I.; Okamoto, S.; Kobayashi, Y.;
aTetrahedron Lett., 1991, 32, 371. 69%
1. PhCHO ,24 h 2. MeOH
I*, CP 1 c 1
d
N O \ M O b
-
If quenched after 1 h:
P Me
h 99%(8% de)
45% yield, 98% de John, J.A. Teirahedron Lett., 2991, 32, 1271. Faller. J.W,; DiVerdi, M.J.;
Me. C
PhH (3 h addition)
HO
6 + bMe
HO
HO
OBn
OBn
(62 38) 80% Rochigneux, I.; Fontanel, M-L.; Malanda, J-C.; Poutheau. k TetrahedronLett., 1991, 32, 2017.
MgCl d
0
Br
1. CeC13 , -2OOC
30min
2.
0
A ,-78'C Bn Bn
Bn-Bn HO Bn
Bn
i-
B n e B : H HO Bn Bn
9%
19%
I . BuLi
Ph$-
2. BuLi-TMEDA
THF 3. PhCHO , 2 h $hen. Y,;Wang, T. Tetrahedron Lett., 1991, 32, 4353.
OH
53%
Alcohol - Alkene
Section 332
359
--
Me
ette. L.A.; Friedrich, D.; Rogers, R.D. J. Org. Chem., 1991, 56, 3841. Philippo, C.M.G.; Vo, N.H. Can. J. Chem., 1992, 70, 1356.
- U & ;
Me$i
)=C=
1.9-BBN, RT 2. n-CsH1lCHO
Me
Me
OH NH?
Gu, Y.G.;
89 %
( 9 8 2 diastereorners)
Tetrahedron Lett., 1991, 32, 3029. 1.1-BuLi ,pentandether -78OC
P
2. +20T
O J1-
HO
3. H30+
94%
Bailev. W.F,; Zarcone, L.M.J. Tetrahedron Lett., 1991, 32, 4425.
J-SiMe3
= C-
ph/\/CHO
TiC14, CHzClz, -95°C 45 min
*
OH 57% Hatakeyama, S.; Sugawara, K.; Kawamura, M.; Takano. S, Tefrahedron Lett., 1991,32,4509. 1. BuLi
2. H,O+
c
HO
Nguyen, T.; IWshLE. Tetrahedron Lett., 1991, 32, 5903.
73%
QSiMe,t-Bu
5 eq. I-BuLi 10 eq. MgBq
Bu
--
OSiMepBu
Lautens.;Chiu, P. Tetrahedron Lett., 1991, 32, 4827.
Me,', =
0 : H
66%
Compendium of Organic Synthetic Methods, Vo18
360
Ph-C=C-H ,SmIz. t-BuOH THF-HMPA ,RT , 5 min
J
Lr
Me
Ph
Section 332
Ph
93%
(%:I4 E:Z)
Inanana.; Kabuki, J.; Ujikama, 0.;Yamaguchi, M. Tetrahedron Lett., 1991, 32, 4921. 1. Dibal, CH2CI2, -78OC 2. EtMgBr ,-78OC - 20°C J
-c
c
0,Me
OH
88%
Marek.; Alexakis, A.; Normant, J-F. Tetrahedron Left., 1991, 32, 5329. 1. MePPh3Qi , BuLi
NHBoc
NHBoc 2. ICH2SiMq
Ph
dCHO
3.TBAF
ph+ (>95:5
OH
65%
syn:anti)
Franciotti, M.; Mann, A.; W d e i. M Tetrahedron Lett., 1991, 32, 6783.
5
CHO BF300Et2 99%
SnBu3 Yamamoto.; Yamada, J.; Kadota, I. Tetrahedron Lett., 1991, 32, 7069. 1. Tack. Zn , DMElPhH
94%
Kataoka, Y .; Miyai, J.; Oshima, K.; Takai. L;m o t o .,(I J. Org. Chem., 1992, 57, 1913. Takai. K,; Kataoka, Y.; Utimoto. K,J. Org. Chem., 2990, 55, 1707. PBQ, THF ,RT 25% DABCO , 1 d
C02Et Roth, F.; Gygax, P.;
Tetrahedron Lett., 1992, 33, 1045.
75%
Section 332
Alcohol - Alkene
36 1
**
1% Bu4N ReO4, CH2CI2 5%p-TsOH*H20,5 min
H 0”’
(2.5: 1 cis:trans) dienes formed with longer reaction times Narasaka; Kusama, H.; Hayashi, Y. Tetrahedron, 1992, 48, 2059.
L
q 2.pph3 1 . ‘a,25,C , CC4
z
~
-
+
-
-
10-20% conversion
(92
8)
Dussault.;Hayden, M.R. Tefrahedron Lett., 1992, 33,451.
J
97%
6 9 5 5 p:m) Singleton. D.A,; Martinez, J.P.; Watson, J.V. Tetrahedron Lett., 1992, 33, 1017. Singleton. D.A,; Martinez, J.P. Tetrahedron Lett., 1991, 32, 7381.
(4:l dr) Rawal. V.H.; Krishnamurthy, V. Tetrahedron Lett., 1992, 33, 3439.
OMe
Ph-
PhCHO [(CpzZrCl2)2/BuLi]
Ph Ito, H.;
.
(10:1 threo:erythro) ;Hanzawa, Y. Tetrahedron Lett., 1992, 33, 1295.
-
362
Compendium of Organic Synthetic Methods, Vol8
Br
Me3Si-
L
, PhCHO
Me3Si*
Br
CrC12, THF , RT , 3 h
Ph
t
/
Me
6Bn
McNeill, A.H.;
-
69%
!%Me3
Hodcson. D.M, ; Wells, C. Tetrahedron Lett., 1992, 33, 4761.
B u 3 S n w
Section 332
Me OH
1. SnC14, -78°C. 5 min
-
B
2. Me B~&, CHO , -7PC
n
o
w
76%
BnO"
(<4% other diastereomers)
TetrahedronLett., 1992, 33, 1369.
x
,,,SnBu3
B uLi
w
OBn 0-
OBn OH 9) 94% Tetrahedron Lett., 1992, 33, 5795. (9 1
Tomooka, K.; Igarashi, T.; Watanabe, M.;
H-Cr C-Bu
1 . CpZZr(H)Cl, CHzC12 RT , 10 min
OH
2. PhCHO
cat. AgC104
Maeta, H.; Hashimoto, T.; Hasegawa, T.; ~ z u k i K, . Tetrahedron Leu., 1992, 33, 5965. 1. LDA , THF , -78°C 2. MesSiCl 3. MeOH ,20"C, lh
Le Nocher, A M . ;
TetrahedronLetr., 1992, 33, 6151.
ph
Me
s.i.ph
Me
2.aq. H F , MeCN
MeOX L.
NaHCO3.1 h RT
Me
Me
1. PhMe (93 mM) 172°C. 24 h c
M~'''' Me02C (1
Craig. D,; Reader, J.C. Tetrahedron Lett., 1992, 33, 6165.
'''rOH Me
Me"' Me02C 1)
Me 75%
Alcohol - Alkene
Section 332
363
1. cu* 2. PhCHO H
83%
3. -c1
Ph
Cu* = zero-vaient copper (from CuCN-2 LCI) Stack, D.E.; Rieke. R.D.Tetrahedron Lett., 1992, 33, 6575. 1. Cp2Bu2, PhMe -78°C -+ RT
7)
2. PhCHO , "X", 3 h -78OC 3. 1N HCI
~
P&
X = no Lewis acid
Ph
+
"1
ox
OH
(35
65) 29)
X = BF3*OEt* (7 1 Ito, H.; B e u chi. T.; Hanzawa. Y. Tetrahedron Leu., 1992, 3. 7873.
Cp2TiCI , THF
70% 82%
OH
b
@+Z)
91%
Yadav.; Shekharam, T.; Srinivas, D.Tetrahedron Lett., 1992, 33, 7973. Yadav.;Shekharam, T.; Gadgil, V.R. .I. Chem. SOC., Chem. Commun., 1990, 843. MeN02 CH3S03Ht 16 h b
75°C
75%
Ph)=N-oH Me
(E+Z)
33% z Blanchot-Courtois, V.; Hanw~I.Tetrahedron Left., 1992, 33, 8087. B,. , AI-InC13 , RT
PhCHO
THF-HzO, 50 h
Araki, S.; Jin, S-J.; Idou, Y.; -Bull.
=
PhCHO -aka.
'*
Bn
SMe
b
OH
&
Ph
88%
Chem. SOC. Jpn., 1992, 65, 1736.
SMe
OH
, BF3eOEt2
CH2C12, -78°C
OH
P
h
V
p
K,; Shibata, T.; Hayashi, Y. Bull. Chem. SOC.Jpn., 1992, 65, 2825.
h 83%
364
Compendium of Organic Synthetic Methods, Vol 8
Section 33-
15)
(85
Fukuzawa. &; Sakai, S. Bull. Chem. SOC.Jpn., 1992, 65, 3308.
97%
I . PhCHO , SnClZ PdCldPhCN)2
-OH
OH i- 9 Ph
15"C,4h 2.
)))>)))))
P
h
RT , 4 8 h
2) 57% (98 (67:33 E:Z) ( 7 0 3 0 syn:anti) Masuvama. Y,; Hayakawa, A.; Kurusu, Y. J. Chem. SOC., Chem. Commun., 1992, 1102.
'r'
1. THF , 160°C, 1 h 2. PdC12(PhCN)2
SnCl2, DMI, HzO
RT,5d
%O
*
OH
35%
(32:68 syn:anti)
Masuvama.;Nimura, Y.; Kurusu, Y. Tetrahedron Lett., 1992, 33, 6477. 1. LDA , r-BuOK
Degl'Innocenti, A.; 1992, 753, 803.
..
; Pecchi, S.; Pinzani, D.; Reginalo, G.; Ricci, A. Syntert,
Allylic and benzylic hydroxylation (C=C-C-H -+ C=C-C-OH,etc.) is listed in Section 41 (Alcohols from Hydrides). Also via: Section 302 (Alkyne - Alcohol).
SECTION 333: ALDEHYDE
- ALDEHYDE
Jlnefa.;Xinhua, X.; Haiying, C.; Anren, J. Tetrahedron, 1992, 48, 3503.
Alcohol - Amide
Section 334
365
OMe
Moeller. K.D.; Tinao, L.V. J. Am. Chem. Soc., 1992, 114, 1033. REVIEWS:
"Oxidative Rearrangement of Fury1 Carbinols to 6-Hydtoxyl2H-pyran-3(6H)ones, a Useful Synthon for the Preparation of a Variety of Heterocyclic Compounds" Georeiadia. M.P,; Albizati, KF.; Georgiadia, T.M. Org. Prep, Proceed. lnt., 1992, 24, 97.
- AMIDE
SECTION 334: ALDEHYDE
0
1.
0
2. silica gel Wasserman. H.H.; Cook, J.D.; Vu, C.B. J. Org. Chem., 1990, 55, 1701. 1. PhMe , NEt3 RT,Sh
Af = 4-(Meo)-C&
Alcaide.;Martin-Cantalejo, Y.; Plumet, J.; Roddquez-L6pez, J.; Sierra, M.A. Tetrahedron Lett., 1991, 32, 803.
Tol0,SHN
&
NBS , DME, H 2 0 , O'C, 2 h ~
OH
N S02Tol
(>9S:S
JPeer. V,; Humer, W. Angew. Chem. Inr. Ed. Engl., 1990, 29, 1171.
dr)
366
Section 335
Compendium of Organic Synthetic Methods, Vol8
r-L ? BOC
q-'* ,NaOCl
OH
NaBr , aq. NaHCO3 ,(lo:
&HO
?J
Boc
82%
(>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%
<4%
Jackson. W.K.; Perlmutter, P.; Tasdelen, E.E. Tetrahedron Leu., 1990, 31, 2461.
(67
33)
76%
Anastasiou, D.; Campi, E.M.; Chaouk, 11.;W o n . W.B.; McCubbin, Q.J. Tetrahedron Lett., 1991, 33, 2211. 1. MeOH ,reflux, 23 h 2 . 6 N HCI , H2O/CH2C12
reflux, 26 h
c1
De Kimne, N.; Boeykens, M.; Boelens, M.; De B'uck. K.;Cornelis, J. Org. Prep. Proceed. Int., 1992, 24, 679. 1. BuLi , -78°C 2. MgBr2, O°C 3. PhCHO , -65OC
Zhang, P.;
50% (80% ds)
Tetrahedron Lett., 1992, 33, 2945.
Aldehyde - Ester
Section 336
PhNHMe ,cat. DBU THF , -15”C, 40 min
dCHO
-
367
P h M e N d CHO
>95%
Mark6. I.E.; Chesney, A. SynLett, 1992, 275. Chesney, A.; M&&LFL Synth. Commun., 1990, 20, 3167. REVIEWS:
“Synthesis of a-Amino Aldehydes and a-Amino Ketones“ Fisher. L.E.; Muchowski. J.M. Org. Prep. Proceed. Int., 1995, 22, 399.
SECTION 336: ALDEHYDE
- ESTER ,?!
1. EIO’ poEl “zEt
M%N-N-,
KzCO3, reflux
CHO 2.H
Kp , H +
*
H< 85%
CO2Et
cH
0
Schmitt, M.; Bourguignon, J.J.; Wermuth, C.G. Tetrahedron Lett., 1990, 31, 2145.
NMe2
OMe Tsay, S-C.; Robl, J.A.;
I. EtOTf ,CHzC12
RT
2 . 2 eq. L-Selectride THF , -78OC
*
69%
OMe
J. Chem. Sac.. Perkin Trans. I, 1990, 757, 1. NaI , Me3SiCl , DMF
Ph 7CHO 2. NZCHCOzMe, NEt3 heat
H q C 0 2 M e Ph 35%
Cu(acac)2 3. NEt3*HF, CH2C12 - Synthesis, 1990, 43. Kunz, T.; Janowitz, A.; IWigJUL 1. e‘ , NaI , MeOH 2.2.F h o l
also for preparation of ketone-esters
Me H7(yCO2Me 0 C02Me 80%
.. . ~G.I.; Elinson, M.N.; Feducovich, S.K. Tetrahedron Lett., 1991, 32, 799.
368
Compendium of Organic Synthetic Methods, Vol8
Section 337
0
k0,Er
EqEt
c4m
(>99
>90%
I)
Gillard, J.W.; Fortin.,G r i m , E.L.; Maillard, M.; Tjepkema, M.;Bemstein, M.A.; Glaser, R. Tetrahedron Lett., 1991, 32. 1145.
HO
To
(Bu3Sn)zO. 80°C
5h
0
0
80%
Shibata.;Matsuo, F.; Baba, A.; Matsuda, H. J. Org. Chem., 1991, 56, 475.
SECTION 337: ALDEHYDE
- ETHER, EPOXIDE, THIOETHER
PhSH , benzophenone
PhS-
hv , MeCN , 1.7;
&hoH
CHO
75%
Gravel.; Farmer, L.; Ayotle. C. Tetrahedron k i t . , 1990, 31, 63.
nCH0
BF3eOEt2, -78°C
0%
*
CH2C12
n-C3H7
0
n-C3H7
74% Frauenrath. H.; Sawicki, M.Tetrahedron Lett., 1990, 31, 649.
BnSH , PhH ,4OoC 12 h
*
PhC-SAcHo
)-CHO
w, Elmaleh, D.R. Org. Prep. Proceed. Int., 1990, 22, 112.
(77
Polo, A.; Real, J.; Claver, C.; Castill6n. 1990, 600.
48%
23)
98%
&; Bay6n. J.C. J. Chem. Soc., Chem. Commun.,
Aldehyde - Halide
Section 338
369
phvph POC13, DMF 80"C,'jh
Ph
phQrHO * OHC
52%
Ph
Venugopal, M.; Umarani, R.; Perumal. P.T.; -R
phm .Ph S 0
Tetrahedron Lett., 1991, 32, 3235.
1. NaOAc ,Ac20 ,Tf20 2. NaHCO3
c
3.5 eq. K2CO3, MeOH
Ph
-Yh
CHO
55%
NH4C 1 Craip.;Daniels, K.; MacKenzie, A.R. Tetrahedron Lett., 1991, 32, 6973.
H-C;C-n-GH17
I I - C ~ H ~ ~ PhH SH, AIBN ,CO(80atm) w n - C ~ 5 ~ 1 3 ~ - C S H l ?
-
n ~ 6 ~ 1 3~un-GH,,
+
100°C
CHO
9%
70%
; I s o e . J . Chem. Soc., Chem. Commun.. 1992, 880.
Nakatani, S.;
SECTION 338: ALDEHYDE
- HALIDE, SULFONATE
-&QPhz?1. n-BuLi ,-78°C
F
HQPh 51%
2.PhCHzBr
76% Patrick, T.B.; Hosseini, S.; Bains, S. Tetrahedron Lett., 1990, 31, 179. 1. iPrNH2
-CHO
2. NCS , CCl4 3. AlC13 , CS2 4. oxalic acid aq. CH2C12
c
TCHO
c1 32%
Stevens, C.; De Kimpe. N. Org. Prep. Proceed. Int., 1990, 22, 589. DMF , PWI3
Evans.;Lloyd, H.A.; LaBeau, D.; Sokoloski, E.B. Org. Prep. Pruceed. int., Z990, 22,764.
370
Compendium of Organic Synthetic Methods, Vol8
13
(84
Section 339
3)
14%
Duhamel.; Guillemont, J.; Poirier, J-M.; Chahardes, P. Tetrahedron t e t t . , 1992, 33, 5051. 1. LDA , THF, 0°C
N'
4
t-Bu 2. Me3SiCI
3. NCS , C C 4 , RT
63% 4. 10 eq. MeOH ,CC14, RT c1 5. (C02H)z. H20-CH2C12 &&mp%&; Coppens, W.; Krauze, A.; De Corte, B.; Stevens, C.; Welch, J. Bull. Soc. Chim. Fr., 1992, IOl, 237.
SECTION 339: ALDEHYDE
- KETONE
l o
[
PhSCH20Me , THF 1. THF BuLi ,-78"C, , -78°C2 h, M
Me M&
e a z o
Me
SBu 2. HgC12, H+
hemf&L; Panilla A.; Camps, F. Tetrahedron Lett., 1990, 31, 1873.
d-H
1. BuLi , THF , -78°C 2. t-BuOzCCI
4.6N 3.n-CsHlsMgBr NH3
OEt
Savoia.;Concialini, V.; Roffia, S.; Tarsi, L. J.
74% Org. Chem., 1991, 56, 1822.
1. PhSeBr ,HgC12, AgN02 2. DMAP
O d
OEt
3.10% HCI
(38%..
(95%)
bCH
Backvall, J-E.; Karlsson, U.; Chinchilla, R. Tetrahedron Lett., 1991, 32, 5607.
Adger, B.M.; Barrett, C.; Brennan, J.; McKervev. M.A.: Murrav. R.W. J. Chem. SOC.,Chem Commun., 1991, 1553.
Aldehyde - Alkene
Section 34 1
37 1
n
SH SH
CK-H
AI2O3.4 h
Ranu. B.C,; Bhar, S.; Chakraborti, R. J. Org. Chern., 1992, 57, 7349.
x
OSiMe2t-Bu
c
70%
c q
' b SnBu3, CAN
MeCN S , MS 4 A , -23°C
87%
Narasaka.; Okauchi, T.; Arai, N. Chern. Lett., 1992, 1229. SECTION 340: ALDEHYDE
- NITRILE
NO ADDITIONAL EXAMPLES
SECTION 341: ALDEHYDE
-
ALKENE
For the oxidation of allylic alcohols to alkene aldehydes, see Section 48 (Aldehydes from Alcohols). I
PhCHO ZnBr;!
ZnCl;!
cat.
SiMe,
THF
& -
N' -hp
aq.ether
Ph
4 C H O
86%
E only
Gaudernar, M.; Bellassoued, M. Tetrahedron Leu., 2990, 31, 349.
'3 !A
1, t-BuOK ,TlIF
0
EtO-
0
2.PhCHO
3. H30+
-
Ph
-CHO
OEt 86% Duhamel. L,; Guillemont, J.; LeGallic, Y.; Pl6, G.; Poirier, J-M.; Ramondenc, Y.;Chabardes, P. Tetrahedron Lett., 1990, 31, 3129.
Kataoka, H.; Watanabe, K.;SkxdL Tetrahedron Lett., 1990, 31, 4181.
372
Compendium of Organic Synthetic Methods, Vol8
Section 341
60%
Jeffew. T. TetrahedronLett.. 1990, 31,6641.
* \
OH
V-PILC ,rn-xyiene
\
reflux, 1.5 h
r C H O
.c
84%
V-PILC = vanadium-pillared montmorillonite clay Choudarv. B.M,; Prasad, A.D.; Valli, V.L.K. Tetrahedron Left.,1990, 31, 7521. 1 . BuLi , THF , -23°C Ph 2. PhCIIO w
3. H2O C C H O 4. KH , 18-crown-6 36%overall THF Enholm.; Satici, H.; Prasad, G. J. Org. Chem., 1990, 55, 324.
r LDA ,THE - 7 8 ~ n-C5H, ,CHO 2.S i q
1
THF.2h
-CHO n-C5H 1 1 (84: 142 all E2E,4Z:2Z,4E)
78%
Kann, N.; Rein. T,; hennark. B,; Helquist, P. J. Org. Chern., 1990, 55, 5312.
iPr d De K-;i
1. NaOMe , MeOH ,heat 2. (COzH)2*2H20, heat H20.CHzCl2
H
--
T
H
O85-95%
Stevens, C. Bull. SOC. Chim. Belg., 1990, 99,41.
(7:93 EZ)
Nonoshita, K.; Banno, H.; Maruoka, K.;
64%
J. Am. Chem. SOC.,1990. 112, 316.
2
37 3
Aldehyde - Alkene
Section 341
&CHO
Mahrwald, R.;
Ti(OiPr)4 , hexane -68"C, 4 h
aSynthesis, 1990, 592. Li
PhCHo
Ph
2.1N HCI
-CHO
Contreras, B.; Puhamel. L.; Ple, G . Synth. Commun., 1990, 20, 2983.
)&
CH2Cl2 ,-78OC c
&CHO+
2090
CHO
73%
(74% ee)
iPr
Takasu, M.; Yamamoto. H. SynLett, 1990, 194.
-
Sartor, D.; Saffrich, J.;
".;q Me
O +0
4 C H O
95%
(c1:99 endo:exo) (64%ee)
SynLett, 1990, 197.
3M LiClO4, ether
(3JcH
co. P A ; Clark, J.D.; Jagoe, C.T. J. Am. Chem. SOC.,1991, 113, 5488.
Me ; 91%ee) (>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 <5)
(295
93%
b r e . G.L;Akgiin, E. Tetrahedron Lett., 1991, 32, 5521.
ph&
hna&~&;
BnNH?. EtOH bake; yeast C02Ec
Ph /
P-cyclodextrin,37"C pH 7 . 2 . 4 8 h
C02Et NHBn 70%
(73% ee)
Nageswar. Y.V.D.; Kumar,H.M.S. Tetrahedron Lett., 1991, 32, 6611.
c0,a
Na2SzOa. AgN03 H2SO4, CH2C12 reflux.1.5h 0 E l 0 5 OH 0
C02Et+ 58% 84% conversion
N 27%
Copa, F.; Fontana, F.; Lazzarini, E.; Jvlinisci. F; Pianese, G.; Zhao. L. Tetrahedron Lett., 1992, 33, 3057.
f i NEt2
d
C02Me
,NMp
Ru(COD)(COT) , 7OoC 20 h
Mitsudo.; Zhang, S-W.; Satake, N.; Kondo, T.;
Me Tetrahedron Lett., 1992, 33, 5533.
404
Compendium of Organic Synthetic Methods, Vol8
1. MeLi
Me $0
Bn-‘ *N
Section 35 1
Ph
2. NaBH4 3’ H2S04
B n - N g ;
0
51%
0
(4:l p:a methyl) Fray, A.H.; Mgyers. A.L Tetrahedron Lett., 1992, 33, 3575. Et02Cy
1. NaHMDS , 2. 1N HCI , RT
-
N=CHPh
Br
WH2 0
COZEt
53%
Kotha, S.; Kuki. A, Tetrahedron Lett., 1992, 33, 1565.
(85
15)
72%
hXliiI&; Marion, P. Tetrahedron Letf.,1992, 33, 5339.
Yamamoto.; Asao, N.; Uyehara, T. .I. Am. Chem.Soc., 1992, 114, 5427. REVIEWS :
;J-
”The Asymmetric Michael Addition Reaction Using C h i d Imines” Desmaele. D.; Dumas, F.; Guingant, A. Tetrahedron Asymnlefry, 1992, 3, 227. Related Methods:
Section 315 (Carboxylic Acid - Amide). Section 316 (Carboxylic Acid - Amine). Section 344 (Amide - Ester)
Amine - Ether
Section 352
405
- ETHER, EPOXIDE, THIOETHER
SECTION 352: AMINE
1. MEGiCl , NEt, 2. TBAF
Y NO2 0-
74% (>99: 1 trans:cis)
Dehaen, W.; Hassner. A. Tetrahedron Len., 1990, 1990, 743. PhCHO Au[c-C&I~1-N=C]zBF4
CO,Me
CHgl2
1
Phwco2M
OWN
cat.
OWN
12)
(89 92% ee
cat.=
1% ee
F~ PPhp. Me
Pastor. S.D. ; Togni, A. Tefrahedron Lett., 1990. 31, 839. baker’s yeast
C1
Ph
pH 7.2 buffer
lower selectivity with ethyl cinnamate or 2.4.6-trimethylphenyl nitrile oxide
Rao.;Bhanumathi, N.; Srinivasan, T.N.; Sattur, P.B. Tefruhedron Leff.,1990, 31, 899, 0‘ Na’
” j f H
Me0
\’
+
DMF. l z p -
, -
Br
%H
\ I H
(4
1)
61%
Grip? R.; Markandu, J.; Surendrakumar, S. Tetrahedron Lett., 1990, 31, 1191.
NHMe
Hg(OAc)2, MeOH,RT AcOH
%Me
Maiumdar.;De, R.N.; Saha, S. Tefruhedron Left., 1990, 31, 1207.
80%
406
Section 352
Compendium of Organic Synthetic Methods, Vol 8
n-Bu. N- H n-B;
n-Bu. 0.15M malonic acid MeCN , t-BUSH
~ /OEt z
n-B;
69%
2. 2.6 eq. =\oEt Newcomb, M.; Kumar, M.U. Tetrahedron Lett., 1990, 31, 1675. 1. 1.5 Hg(0Ac)z
MeCN , 25°C R2
2.3. P aq. 2 NaCl LiBH4
THF , - 7 R T
&Dz2 0
0
Me
-I- e
3
Me
,
0
t
R
2 R'
0
R' = OBn; R 2 = H (>50 1) 89% R' = H;R~ = O B ~ ( I >50) 78% Helle, M.A.; Sanyal, B.J.; Eberspacher, T.A. Tetrahedron Lett., 1990, 31,6765. PhCO3H, BnEt3NCI CH2C12 - H 2 0
M e 4 N<
*
85-95%
0
Balachkova, A.I.; Koldobskii, (3.1.; Drozdetskii, A.G.; Tereshchenko, G.F. Zhur. Org. Khim., 1990, 26, 216 (En& p. 185).
3Me
0, Me_
OH
n-BuLi-t-BuLi THF , KT
Me,
Me
(85
15)
Roussi.;Zhang, J. Tetrahedron Lett., 1991, 32, 1443. d
O N
M
e
saPh 0
MewMe
-oo+ oo =d-
80%
&gBr_
THF
79%
Me0
Shibutani, T.; Fujihara, H.; Furukawa. N. Tetrahedron Lett., 2991, 32, 2943.
Amine - Ether
Section 352
@
%Ygl,,Me*
w
0.004 M
407
yNo58%
0
Boner.;Yohannes, D. J. Org. Chem., 1991, 56, 1763.
Ph
H o
MezNCH(0Me)z DMF ,PhH , reflux
{IMe HzNgoH OH
81%
Ph
Amberlite , 1 6 h
c&
Leonard, W.R.; Romine, J.L.; Meyers, A.I. J. Org. Chem., 1991, 56, 1961.
N
.Bu
TiC13(0iPr) , CHzC12 -78°C
\/\//
98%
Newcomb.; Ha, C. Tetrahedron Left., 1991, 32, 6493. J F - B u Me,Si'
OMe
BuLi , THF
*
N
BuCuMgBrbBF3 THF , MDS
OMe
B u d M e NH2
B u g M e NH2
i-
(2
*
98)
46%
1)
54%
(99
Cainelli. G,; Giacomini, D.; Panunzio, M.; Zarantonello, P. Tetrahedron Letf., 1992, 33, 7783. ( W 2 x
>A;o.tone 0
(W2NJ t
05 0
93%
N(iPr)2
Adam.;Peters, E-M.; Peters, K.;von Schnering, H.G.; Voerckel, V. Chem. Ber., 1992, 125, 1263.
REVIEWS:
"Preparation of Diaminoethers and Polyamines" Bradshaw. J& ; Krakowiak, K.E.;Izatt, R.M. Tetrahedron, 1992, 48,4475.
408
Section 353
Compendium of Organic Synthetic Methods, Vol8
SECTION 353: AMINE
- HALIDE, SULFONATE Ph-CTC*
OMe Ph
0 CF3
Me0
NH2
"FA, reflux 2h
Me0
48% Linderman.;Kirollos, K.S. Tetrahedron ,!,ell.. 1990, 31, 2689.
1)
76%
Friesen. R.W, Tetrahedron Lett., 1990, 31, 4249. AcCl , NaI , MeCN reflux, 24 h 55%
Corcoran.;Bang, S.H. Tetrahedron Lett., 1990, 31, 6757.
0
AcOF ,CH2Br2
N
kfi
Hebel, D.; Ibzen.3 J. Org. Chem., 1991, 56, 6298.
0-
1. PhOPh , reflux 2. wc13
MeskCN N
N
Br
60%
c1
C02Me
49%
SMe
H
Tominapa. Y,; Michioka, T.; Moriyama, K.;Hosomi, A. J. Her. Chem., 1990, 27, 1217. MesSiN3 ,CH2C12-MeN02 NBS , -5°C + RT
or3 67%
Olah.;Wang, Q.; Li. X-Y.;
SynLett, 1990,487.
Amine - Ketone
Section 354
t-Bu C1
409
BH3*SMe2, CH2Cl2
H
reflux, 7 h
C1
w; Stevens, C. Tetrahedron, 1991, 47, 3407.
,$
N yN
1. benzyne ,dioxane
reflux, iAmONO
2.aq. KOH
C1 Cl Gonsalves, A.M.d'A.R.; Pinho e Melo, T.M.V.D.; Gilchrist, T.L. Tetrahedron, 2992, 48, 6821.
-
SECTION 354: AMINE
KETONE
____c
3h
Bn NHBn 65% Vatele, J-M.; Dumas, D.; Gore, .I. Tetrahedron Lett., 1990, 31, 2277.
-
OH
NaH , PhH 80°C
88%
Br
Wassenan.;Cook, J.D.; Vu, C.B. Tetrahedron Lett., 1990, 31, 4945. 1. NaN(CHOh, EtOH RT --f 50°C 2. HCI , reflux
Br Ph Yinglin. H.; Hongwen, H. Synthesis, 1990, 615.
*
0
a,
" 2. PhMe , reflux
Ph
0 b
Ph
+q+ P
Ph
12
:
(0.67
q
H'
11
1)
95%
Cordero, F.M.; Brandi. A,; Querci, C.; Goti, A.; DeSarlo, F.: Guarno, A. .I. Org. Cheni., 1990, 55, 1762.
Compendium of Organic Synthetic Methods, Vol8
410
0
iPr
1. LDA ,THF ,0°C
*
2. PhCO2Me , THF 0°C
0
NHiPr 68%
Ph
Bartoli.;Cimarelli. C.; Palmieri, G.; Bosco, M.; Dalpozzo, R. Synthesis,
N i3
N
i3
Kraus. G.A,; Shi, J. J. Org. Chenz., 1990, 55, 5423,
Et2N-
73%
Et2Ny
t-BuOK ,DMSO
0
1990, 895.
Meo2C+pph
-78°C PhLi ,+ THF OoCw
Me02cf&Br
Section 354
52%
Arenz, T.;
Angew. Chetii. Int. Ed. Engl., 1990, 29, 932.
0 Br
0 p
%
0 NEt3
CO2R
nIchihara, ; Y.; Mori, T.; Kamio, C.;
46%
Et02C '
J. Het. Chem., 1990, 27, 263.
Noien. E.G.; Ailocco, A.; Vitarius, J.; McSorely, K. J. Chem. Snc., Chetn. Cotnmun., 2990, 1532.
A
DCA = 9,10-dicyanoanthracene
Jeon, Y.T.; Lee, C-P.; Mariano. P.S. .I. Am. Chem. Soc., 1991, 113, 8847.
Amine - Ketone
Section 354
41 1
3 eq. [3 THF-Mg2C120-TiNCOI 5% Pd(PPh3)4, NMP, 12 h
6
\
100°C
Uozumi, Y .; Mori.;
Me
0
'
* b
H
e 87%
4'
J. Chem. Soc., Chem. Commun., 1991, 81.
BnNH2, AcOH , PhMe reflux
Me
67%
NHBn
Synthesis, 1991, 1 IS.
Otto, A.;
M
%
1. BnNH2, CH2CI2
MeOH
2. NaOMe , MeOH
N Bn
65%
a o u . S-S.E; Yuan, T-M. Synthesis, 1991, 171.
0
Ph
NHiPr
AA
1. LiTMP , THF , 0°C 2.MeI
0 4
Ph
NHiPr Me
86% Bartoll.;Bosco, M.; Cimarelli, C.; Dalpozzo, R.; Palmieri, G. SynLett, 1991, 229.
Baxter, G.; Melville, J.C.; Robins. D.J, SynLea, 1991, 359.
OBBU, P
h
k
+
M%Ny
NM%
0
CHzClz
P h v P h Me
Ph -78'C
33%
(4
0
NMe2 +
NMe2
P h v P h Me
RT 95% (1 Nolen. E.G.; Allocco, A.; Broody, M.; Zuppa, A. Tetruhedron Lett., 1991, 32, 13.
1) 17)
412
Section 354
Compendium of Organic Synthetic Methods, Vol 8
a
Ph-CGCH , CO 5 % PdClz(PPh3)~
I
NH2
Et2NHt 120°C 6h
Ph
H
90%
Toni.;Okumoto, H.; Xu,L.H. Teiruhedron Left., 1992, 32, 237.
JyJ
0
Phl(OzCCF3)2 CF3CH20H RT ,30 min
N
H
b@JJ
o
H o
51%
J(ita. Y.;Tohma, H.; Inagaki. M.; Hatanaka, K.; Kikuchi, K.; Yakura, T. Tefrahedron Leff., 1991, 32, 2035.
1. TNHTos
(CO),CO
OH
BFyOEt2, -7EC CHzClz 85% 2. Me3N-0,Oz CHzC12 , RT , 1 h Jeonc. N.; Yoo. &; Lee, S.J.; Lee, S.H.; Chung. Y.K. Tefruhedron Lett., 1991 32, 2137.
co
Q b
l.PhCH0,
GNH2
conc. HCI 2.10% aq. NaHC03
H\
P
I
h
88%
Yi, L.; Zou, J.; Lei, H.; Lin, X.; Zhang, M. Org. Prep. Proceed. Inf., 1991, 23, 673.
Ph
kc
Ph
e- (graphiteelectrodes) MeOH , PhH ,NaOH (-1.78 V) , 30"C, 8 h*
Ph
hPh 65%
H
Rajanarayanan, A,; levaraman. R, TefruhedronLeft.,1991, 32,3873.
Amine - Ketone
Section 354
413
(98
De Kimne. N,; DHondt, L.; Moens, L. Tetrahedron, 1992, 48, 3183. P h - C S - H , PdCl2(dppf) COEtzNH (20 atin) ,autoclave , 120°C. 1 h
*
2) ‘ 1 2 %
dph 70%
H Kalinin. V.N,; Shostakovsky, M.V.; Ponomaryov, A.B. Tetrahedron Lett., 1992, 33, 373.
4
0si(ipr)3
5 eq, NaN3 5 eq. CAN
-
&N’
72%
Maenus. P.; Barth, L. Terrahedron Lett., 1992, 33, 2789. Bn.
PhMe , R O T , I h
*
BiiHN
UO%
Desmaele, D.; Champion, N. Tetrahedron Lett., 1992, 33, 4447.
Ded’Innocenti.~.; Capperucci, A,; Reginato, G.; Mordini, A; Ricci, A. Tetrahedron Lett., 1992, 33, 1507. 1,
Bu BCI,
.PhMe. 12h
-78°C - RT
2. BnN3 3. MeOH
Noiret, N.; Youssofi, A.; Carboni, B.; 1105.
+
D,”””“ Bu
72%
.I. Chetn. SOC.,Chem. Cotntnun., 1992,
Section 356
Compendium of Organic Synthetic Methods, Vol8
414
REVIEWS :
"Synthesis of a-Amino Aldehydes and a-Amino Ketones" Org. Prep. Proceed. Int., 1990, 22, 399. "Further Advances in the Chemistry of Mannich Bases" Tramontini, M.; Angiolini, L. Tetrahedron, 1990, 46, 1791.
a
- NITRILE
SECTION 355: AMINE
1. hv ,02, DAP+2 (visible light)
2. Me3SiCN , 1 h
H
DAP+2 = N,"-dimethyl-2,7-deazapyrenium bis-tetrafluorohorate 90% Santamaria, J.; Kaddachi, M.T.; Riglaudy, J. Tetrahedron Lett., 1990, 31,4735.
phxN-Ts
2 MeqSiCN ,THF 0.5 Yb(CN)3,65"C Ph 3h
Matsubara, S . ; Kodama, T.; Utirnoto.
SECTION 356: AMINE Ph ph)=
TsHN Tetrahedron Lett., 1990, 31,6379.
- ALKENE
1. Ph3P=CHEl, PhMe
Ny C02t-Bu
ooc
2.2S°C,30 min
0
Nx
Ph ph);
Cost-Bu
85%
O'Donnell, M.J,; Arasappan, A.; Homback, W.J.; Huffman, J.C. Tetrahedron Lett., 1990, 31, 157.
'NHNMez
@ PhjP-
1. I-BuOK, THF 2. ~ - C ~ H I ~ C H O wn-C7H 15
350C.20h
B P yields lower with ketones J=ristau. H.-J,; Gasc, M.-B. Tetruhedron Lett., 2990, 31,341.
-
MQN+ E
N
-
H
N G B ~
Et 85:15
% - N- NMe,
H
80%
1. scc-BuLi 2. BrCHzCH=CH2
Nt-Bu 3.N2H4 or LiAIH,
Beeley, L.J.; B f z M U J X Tetruhedron Lett., 1990, 31,417.
Z:E
39%
Amine - Alkene
Section 356
-0
K 0
(PhCH&NH OOC, 9 0 h
OMe
PPh,
-
415
+
NBu,
3)
(97 84%ee,S
&eH Ph2P
-NBu, 87%
91:9 E:Z
:
N Me
OH
HO*
Havashi. T.; Kishi, K.; Yamamoto, A.;
Tefrahedron Letf., 2990. 31, 1743.
OTf
N(Boc)2
B u ~ N,DMF ,80"C 5% Pd(OAc)*(PPh3)2 5h
36%
Arcadi, A.; Bernocchi, E.; Cacchi, S.; Caglioti, L.; Marinelli, F. Tetrahedron Letf., 1990, 31, 2463.
>
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$-Bu ?h , 2OoCc Q Ph
OSiMe,
Ph
+
P
OSiMe-,
better selectivity-lower yield with AlCb
Ph
OSiMe3
(54
28)
86%
e
92%
Nogue, D.; Paugam, R.; Wartski, L. Tetrahedron Lett., 1992, 33, 1265. 1.9-BBN
Me3Si
N @ CHO
Me)=C=
W
3. NaOOH , 1 h
(98:2
M Z:E)
Tetrahedron Lett., 1992, 33, 5025.
Sattsangi, P.D.;
SiMe3 c
Et
hv , DCN , MeCN:H20 10 h
70%
Pandev. G,; Rani, K.S.; Lakshmaiah, G . Tetrahedron Lett.. 1992, 33, 5107. 1. CF3S03H , 0°C
CH2CI2
b
2. NaOH
&won. N!.H.; Schkeryantz, J.M. Tetrahedron Lett., 1992, 33, 5291.
71%
Amine - Alkene
Section 356
<
Davis, J.M.;
1. Cp2ZrCl2 , 2 BuLi , THF , -78OC 2.n-C3H7 CS C- n-C3H7 , THF
PhNC ,20°C 4 6 7 T , 3 h
H
n-C3H7
4. 3.MeOH H20 ; Jaxa-Chamiec, A. Tetrahedron Lett., 1992, 33, 5655.
Ph Ph
423
56%
NHPh
6Br
D
In,THF, 1 h
91%
Ph
Beuchet, P.; Le Marrec, N.; Mosset. P. Tetrahedron Lett., 1992, 33, 5959 1. CpzTiMe2, PhH
PCN
60°C. 5 d
2.Na2S04
quant.
Barluenea.;del Pozo Losada, C.; Olano, B. Tetrahedron Lett., 1992, 33, 7579. Sm,SmI*,THF . 4 h
&N
67°C
Ph
(78162
72%
EIZ)
Opawa.;Takami, N.;Sekiguchi, M.; Ryu, I.; Kambe, N.; mods. N,./. Ant. Chem. Soc., 1992, 114, 8729.
PhNHOH ,dioxane , 100°C MoOl(dipoc)(HMPA), 8 h
II
NHPh
52%
d i p = 2.6-pyridinedicarboxylate Srivastava, A.; Ma, Y . ; Pankayatselvan, R.; Dinges, W.; Nicholas. K.M,.I. Chem. Soc., Chem. Commun.. 1992, 853.
I . TaC15, Zn , DME PhH 2. MeqAI THF
.
4.aq. NaOH
Takai.;Miwatashi, S.; Kataoka, Y.;
H-N.
NMe2
Chem. Lett., 1992, 99.
80%
424
Section 357
Compendium of Organic Synthetic Methods, Vol 8
1. BuLi
2. CpaZrMeCl ,59"C, 6 h
PhHN--(
3. n-C3H7C&n-C3H7 4. MeOH
phH 92%
Coles, N.; Whitbv. R.L; Blagg, J. SynLeft, 1992, 143. 3 eq. (CH201, , MeCN 6 eq. BudNI, 80°C
NHBn CI C-Me
1.3 eq. MeSO$l
&Me 1
+
62% Ovennan. L.E.; Rodriguez-Campos, I.M. SynLeff, 1992,995.
Bn"D 9%
REVIEWS: "Diels-Alder Reactions of Azadienes: Scope and Limitations" Boeer. D.I, Bull. SOC. Chim. Belg.. 1990, 99, 599. "ElectronicallyNeutral 2-Aza-1,3-dienes: Are They Useful Intermediates in Organic Synthesis?" B a r l u e n m l ; Joglar, J.; GonzAlez, F.J.; Fustero, S. SynLerr, 1990, 129. "The aza-Wittig Reaction in Heterocyclic Synthesis" Emchi. S,; Matsushita, Y.; Yamashita, K. Org. Prep. Proceed. lnr., 1992, 24, 209.
SECTION 357: ESTER
- ESTER Pd(OAc)2, NEt3 , MeCN CO , RT ovenlight
Me &LU&&&;
80%
0
Langlois, P.; Okano, T.; Ozbalik, N. Terrahedron Lett., 1990, 31, 325.
u; Jung, K.W.; Kim, Y.S. Tetrahedron Lea., 1990, 31, 1023.
10%
Ester - Ester
Section 357
425
Me
0
H
(1
Bode, H.E.; Sowell, C.G.;
1)
Tetrahedron Lett., 1990, 31, 2525.
>
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
Ann. Chem.. 1992, 305.
SECTION 359: ESTER
-
HALIDE, SULFONATE
reflux hv (sunlamp)
62%
I Bar& F.; 0 - Y a m . C. Tetrahedron Lett., 1990, 31, 1121.
q
Ph
Ph
4
e' , 3F/mol, NEt3
M e 0 &oQ
3HF-MeCN 65% (60%de)
Kabore, L.; Chebli, S.; Faure, R.; Laurent, E.; Marquet, B. Tetrahedron Lett., 1990, 31, 3137.
r3f/
30% CuCl , MeCN llO°C1 16 h
0
0
Pyrex tube (capped)
99%
m s h i m a , H,; Seki. K.; Ozaki, N.; Wakamatsu, H.; Itoh, K.; Tomo, Y.; Tsuji, J . J. Org. Chem., 1990, 55, 985.
Ester - Halide
Section 359
433
1. BulP=CFC02Et, THF
n-C7HI5-Br
-7 8°C w H-C~HI~CFHCO~E~ 2. aq. NaHCO3 Thenappan, A.; lh&nJLL J. Org. Chem, 1990, 55, 231 1.
0
CF,
ether, reflux
C02Et
2. TBAF ,THF
83%
Shi, G.; Xu. YiJ. Org. Chem., 1990, 55, 3383. Ca(OC1)2, AcOH CH2CI2, H 2 0
>=(c,,t
w
m h e w . L;Alink, B. J. Org. Chea., 1990, 55, 3850.
0 0
OH Me Me
4''
c02et 80%
1. Tf20*NEt(iPr)2 CH2C12 , -78°C 2. PhI(OAc)Z, hv
Kaino, M.; Naruse, Y.; Ishihara, K.; TFA , CuC12
Pb(OAc)4
*o
I Me
J. Org. Cheni., 1990, 55, 5814.
O,CCF,
"'c1
83%
Serguchev, Yu.A.; Gutsulyak, R.B. Zhur. Org. Khim., 1990, 26, 2066 (Engl., p. 1784).
OCO~H
CHC13, iPr2NEt DMSO-TMSBr reflux,l2h
/\1-0 B
r
/-
q 0
55%
Iwata. C,; Tanaka, A.; Mizuno, H.; Miyashita, K. Heterocycles, 1990, 31, 987.
OSiMe,t-Bu
40n-C~H17
60%
CHBr3, BEt3,1.5 h
C02n-CBH 17
Sugimoto, J.; Miura, K.; Oshima. K.; Utimoto. K. Cheni. Left., 1991, 1319.
434
Compendium of Organic Synthetic Methods, Volt?
0
12, aq. THF ,RT c
n-c6H,3+e2
HO
HO
ICFzCOzMe , DMF Cu,6h
Me
I)
cc'
+
-
OH &Me
, , C02Me
.
.
(23:l cktrans)
T. Chem. Lett., 1991, 177.
1. LDA , THF , -78°C 2. THF , -78°C
Ph
&.
y C02Me + F
Ph F
(95
F
Q&&ULE.;
-1v70 ,,,,,
/(0x0
1 Kitagawa, 0.; Sato, T.; -chi.
79%
CF2C02Me
1 . Ti(OiPr)4 , 0°C , 2 h 2. NIS , CH2C12
CO,H
C02Me F 5)
0 2
Riiegg, G.M.; Lang, R.W. Tetrahedron Lett., 1991'32, 1779. 1. LDA , THF, 0°C
Me
)- C02Et
Ph
Resnati, G.; Des m
60%
(5:3 trans:cis) Cheni. Len., 1990, 1011.
'
Kitagawa, 0.;Miura, A.; Kohayashi, Y.;
--I (7
Bpw;tLzE;Li, X . Helerocycles, 1990, 31, 1205.
Ph
Section 359
2. (CF3SO2)2NF -80°C
MexC02Et Ph
a1
u . D.D.J. Org. Chem., 1991, 56, 4925. ICF2C02MeI Cu 55°C
-
F
83%
CF2C02Me
Yang, Z-Y.; l2umJU J. Org. Cheni., 1991, 56,5125. Yang, Z-Y.; J. Chem. Soc., Chem. Commun.. 1992, 233.
78%
40%
435
Ester - Halide
Section 359
q+
TMPAP ,dioxane
Q:,k
RT
0 TMPAP = trimethyl(pheny1)ammonium perbromide
0
52%
Collado, I.G.; Massanet, G.M.; Alonso. M.S. Tetrahedron Lett., 1991, 32, 3217.
fl-
AgN03. Br2 NaOH , MeCN/H@
Br
74%
c
C H
NBS , KHC03 CH2C I f l 2 0
*
CO2H
93%
Dai, W.; J
6
C02Et
Br-
/
60%
Hirao. T,; Fujii, T.; Miyata, S.; Qhshiro. Y,.I. Org. Chern., 1991, 56, 2264.
0
F:%
Ph
1. PhLi ,ether , -78T 2. HgO , I , , PhH w
3. hv , 2 5 T
0
Kobayashi, K.; Sasaki. A,; Kanno, Y.; Sueinome. H . Tetrahedron, 1991, 47, 7245.
\CO2H
1. Br2 , PBr3,120°C, 6 h 2. CH2C12, PhSH , RT 16 h
b.11-J.; Luo, W.Synth. Commun., 1991, 21, 2097. THF 1% BPO ,170,reflux AIBN
Eto*c*FF Me ;-
12 h
0
Br
Eto2c&
c
BPO = benzoyl peroxide Burgess, J.P. Tetrahedron Lett., 1992, 33, 1683.
73%
Compendium of Organic Synthetic Method", Vol8
436
Ti(Ot-Bu)d, 12 CH2CI2,RT
COzMe A
C
0
2
M
e
-
C02Me C02Me
ct,
74%
I
Kitagawa, 0.;Inoue, T.; XagwKL ' Tetrahedron Lett., 1992, 33, 2167.
-
Section 359
Fuchimmi. T.; Hayashi, T.; Konno, A. Tetrahedron Lett., 1992, 33, 3161. Cu(bpy)CI , reflux
O
K
CHC1, PhH (0.1 M) , 18 h
0
G
C
l
92%
E:Z) Pirmng, F.O.H.; Steeman,W.J.M.; JkmuaJL ;;Kaptein, B.; Boesten, W.H.J.; Schoemaker, H.E.; Kamphuis, J. Tetrahedron Lett., 1992, 33, 5141. (70:30
IBr , PhMe , -80°C *
I&
- 1 (21. I Duan, J.J-W.; Sprengeler, P.A.; smith. A.B.
1) 89%
Tetrahedron Leu., 1992, 33, 6439.
% - Go$
1. MezNEt , THF , -78°C
G
C Br
l
2.
HO
c1(85% dr)
Durst, T.; Koh, K, Tetrahedron Lett., 1992, 33, 6799. DMF (1M HCI) , RT oxone, 1 h Kim, J.N.; Kim, H.R.; Pvu. E . S Synth. Comrnun., 1992, 22, 2521.
71%
F
'
h0 q
437
Ester - Ketone
Section 360
C1 P h A P h
BzCI , BuzSnCl~PPh3 7OoC , 15 h
OBz P h A P h
OBz
0 SnCI2, PPh3, BzCl 70T. 11 h
+
(87
80%
13)
99)
(1
t
c1
0
58%
Shibata I,; Yoshimura, N.; Baba, A.; Matsuda, H. Tetrahedron Leti., 1992, 33, 7149. CH2(C02Et)2
TPh OH
C02Me
Me02C
NaH,THF,2S°C 2h
Ph (2
3)
66%
Lawrence, R.M.; I W m W B L Chem. Letf., 1992, 305.
SECTION 360: ESTER
- KETONE "zMe
?Po
Mn(0Ac)s
C U ( O A C ) AcOH ~, 25"C, 3h
61%
H
CO2Me
Method extended to include formation of bridged molecules White.;Somers, T.C.; Yager, K.M. Tetrahedron Lett., 1990, 31, 59.
OMe Me0 2. aq. NaHC03
Me0
C02Me 0 Me Me 60%
Collins. D.L; Dosen, M.; Jhingran, A.G. Tetrahedron Left., 1990, 31, 421.
Ph2S2, AIBN
Ph PhCl , hv (sunlamp)
C0,Me (1
Feldman. K.S.; Vong, A.K.K. Tetrahedron Lett., 1990, 31, 823.
C02Me 1)
46%
438
Section 360
Compendium of Organic Synthetic Methods, Vol8
0
PhI(0H)OTs
CHzCl2 ,reflux* 15h 0 Moriartv. R.M,; Vaid, R.K. Hopkins, T.E.; Vaid, B.K.; Prakash, 0. Tetrahedron Lett., 1990, 31, 201.
Ph
C02H
1.03
74%
,CH2C12 , MeOH -78°C
2. PhH , CH2C12,0°C
A
C
O
SnC12
2
E
63% 0
Holmquist, C.R.; Roskamo. E.L Tetrahedron Lert., 1990, 31, 4991. 1.
PPh3
(
C02r-BU
COZt-Bu
2. oxone, aq. THF RT
86%
Wasserman. H.H,; Vu, C.B. Tetrahedron Lett., 1990, 31, 5205. 1. LDA , THF , -78°C 2. PhzSiClz
$,,
C02Me C02Me
0
4. PhH , reflux , 4 h 5. KH , MeOH
61%overall
intramolecular Diels-Alder using a "disposabletether" Shea. K.J.; Zandi, K.S.; Staab, A.J.; Cam, R. Tetrahedron Lett., 2990, 31, 5885.
72%
CO2H Karim, M.R.; $amn son. P, J. Org. Chem., 1990, 55, 598.
0
t
Ester - Ketone
Section 360
439
HI, AczO, RT
0
0
quant.
Zoeller. J.R.; Ackerman, C.J. J. Org. Chem., 1990, 55, 1354.
Q
1.
Br
2. TMSI , HMDS -20°C -+ RT 3. HC104, aq. THF Eto2C 76% v. T.; Heard, N.E.; Fleming, A. J. Org. Chem., 1990, 55, 2570.
e- (4 F/mol) TMS-CI-DMF
6
76%
CO2Et
W o . T.; Kise, N.; Uematsu, N.; Morimoto, S. J. Org. Chern., 1990, 55, 5037.
0
0
(2
3)
84%
Crandall, J.K,; Rambo, E. J. Org. Chem., 1990, 55, 5929.
EtO2C
0
k
M e O K 0 y 0 ~
CO2Et
Pd(OAc)2, PPh3 , THF reflux , 4 h
Ikeda, I.; Gu, X-P.; Okuhara, T.; -Synthesis,
0 &C02Et
Bu
1. NaOEt ,EtOH 2.03
3. Me2S
Si, Z-X.; Jiao, X-Y.; Hu, B-F Synthesis, 1990, 509.
c
EtO2C
CO2Et
1990, 32.
0 BuAC02Et
48%
84%
440
Section 360
Compendium of Organic Synthetic Methods, Vo18
~
&
1.2 eq.MeLi ,THF , HMPA 2. BnBr ~ ~ ~
*
0
2
t
3.H' Ph/ J I C 0 2 M e 57% 4. CH2N2 Tapia, 1.; Alcazar, V.;Moran. J.R.; Caballero, C.; Grande, M. Chem. Lett., 1990, 697.
Me
Po
Scholz, G.; Konusch, J.; Tochtermann. W, Liebigs Ann. Chem., 1990, 593.
SePh
63%
d C02Me
Bu3SnH, AIBN
C02Me
1990, 112, 4003, 4008. Boger. D.L,; Mathvink, R.J. J. Am. Chem. SOC., B e e r . D.L; Mathvink, R.J. J. Org. Chem., 1992, 57, 1429.
Me 0 Me%J 0
1. LDA ,ether
Ph
2. *e&C02Me,
0
-100°C
* Me+C02Me Me
" )Me CN 4. 3. aq. CuSO4, NH&IH2O Me'
60%
(93% ee , R)
p,,,,8
Enders.;Gerdes, P.; Kipphardt, H. Angew. Chern. Int. Ed. Engl, 1990, 29, 179. 0 ~
&f$H$g
.c
/ C
O
Z
reflux M
~
0
H
+
C02Me
HO
(90
1)
82%
Enholm. E.L; Kinter, K.S. J. Am. Chem. SOC.,1991, 113, 7784.
n-CTH ISCHO Chen, C.; Q&&J,
1. Zn , 'IMF 2. AQO, Py 3. NBS , AgOAc
+
OAc 0
4. t-BuOOH , OsO,, MeOH n-C,H,s epichlorohydrin J. Chem. SOC.,Chem. Commun., 1991, 1289.
C02Me 60%
44 I
Ester - Ketone
Section 360
MeoA
1. PhC02Me , Tic14
Et
CHzCl2 Et 2. MeOH , -78°C 4 0°C * Me02C V 3. NEt3
OMe co2Et
OMe e10 OMe P h i- Me0,C Ph C02Et c0,Et 0%
90%
Shimada, S.; Saigo, K.; Hashimoto, Y.; Maekawa, Y.; Yamashita, T.: Yamamoto, T.; Hasegawa, M. Chem. Lett,, 1991, 1475.
)-CHO
1. (C02Et)z ,NaOMe , 2 h
MeOH , 10°C
2. conc. HCI ,RT , 1 h
Ham. H.; Morishita, T.; Akutsu, S.; Kawamura, M. Synthesis, 1991, 289.
3
Fujimura, T.; Aoki, S.; J%kamura. E. J. Org. Chem., 1991, 56, 2809.
C02a
z:; fi
1. LiN(SiMe3)z
-785
N M 2.~ aq.~HC1
Ph
0
0
CqEt 63%
with NhOAdAcOH at 60°C
McComb ie. S.W,; Metz, W.A.; Nazareno, D.; Shankar, B.B.; Tagat, J. J. Org. Chem., 1991, 56. 4963.
Schinzer.; Kalesse, M. Tetrahedron Lett., 1991, 32, 4691.
Antonioletti, R.; Bonadies, F.; Monteagudo, E.S.; Scettri, A. Tetrahedron Lett., 1991, 32, 5373.
442
Compendium of Organic Synthetic Methods, Vol 8
PhI(OAc)z, I2 CHzC12 ,hv (Pyrex)
+
w a s . P.; Millan, S.D. Tetrahedron Lett.. 1991, 32, 7493.
Section 360
&
54%
hz:Me3
,TASF ,-78°C
64% TASF = tris(dime~y1amino)sulfonium trimethyl difluorosiliconate Klimko, P.G.; m e t o n . D.A, J. Org. Chem., 1992, 57, 1733.
C02Me
1. TosN3 , A1203 KF , THF , RT
4
2. Rhz(OAc)4, RT
OMe
C02Me 46%
Ceccherelli, P.; Curini. M.; Marcotullio, M.C.; Rosati, 0. Org. Prep. Proceed. Int., 1992, 24, 497.
.
Me
NMO C02(CO)6 CHzC12,5 h
0
m
Krafft.,Romero, R.H.; Scott, I.L. J. Org. Chem., 1992, 57, 5277.
I
Bu3SnH, AIBN PhH , reflux C02Me +
Dowd. P.; Choi, S-C. Tetrahedron, 1992, 48, 4773. Dowd. P,; Choi, S-C. Tetrahedron Lett., 1991. 32, 565.
66%
443
Ester - Ketone
Section 360
2%Rh2(TPA)4
CYC12,O"C. 1.5 h
N2
C02Me
C02Me
C02Me
"PA = triphenyl acetate (96 Hashimoto, S.; Watanabe, N.; i Tetrahedron Lett., 1992, 33, 2709. Hashimoto, S.; Watanabe, N.; mi. S, Tetrahedron Lett., 1990, 31, 5173.
4)
75%
68%
Sartori. G.; Bigi, F.; Tao, X.; Casnati, G.; Canali, G. Tetrahedron Left., 1992, 33, 4771. 1 . pyrrolidine
2. LDA , THF
3. Me1 ,-78OC + RT 4. H30+
Hodgson, A.; Marshall, J.; Hallett, P.; W g h er. T. J. Chem. SOC.,Perkin Trans. I, 1992, 2169. Kh4n04*CuS04*5 H20 cat. H 2 0 , CHzClz, 7 h
47 96
0
6
Baskaran, S.; Islam, I.; Vankar, P.S.; Chandrasekaran. S. J. Chem. SOC., Chem. Commun., 1992, 626.
PhI(OzCCF3)2, MeCN
ooc
COZH
83%
k0 0
McKillop. 4,; McLaren, L.; Taylor, R.J.K.; Watson, R.J.; Lewis, N. SynLett, 1992, 201. Also via Ketoacids Hydroxyketones
Section 320 (Carboxylic Acid - Ketone) Section 330 (Alcohol - Ketone)
444
Compendium of Organic Synthetic Methods, Vol8
SECTION 361: ESTER
Section 362
- NITRILE
iPrOH, CH2C12
CN ~ 0 2 ( ~ ~ ) 8 ~ 1 3 OCN 0 C CN
d
200 bar
*
+
NC-CO~~P~
q c o 2 89% i p r
8%
Sisak.;U n g v w , F.; Markb, L. J. Org. Chem., 1990, 55, 2508.
C02Me
1. BuzCuLi , THF -30°C 2. BuBr
Me
* T
M
e
80%
Calb.;Lopez, L.; Pesce, (3. Gazz. Chim. Iial., 1990, 120, 203. CICH2CNt DMSO
PhCOOH
NazCO3
c
PhKOwCN 0
97% Bvers. J.H.; Baran, R.C.; Craig, M.E.; Jackson, J.T. Org. Prep. Proceed. Int., 1991, 23, 373. CICH2CN, NEt3
PhCOOH 80%
+
+
PhCO2CH2CsN 90%
Na2S ,aq. acetone
Hupel.;Bhaskar, K.V.; Longmore, R.W. Synth. Commun., 1992, 22, 693.
SECTION 362: ESTER
- ALKENE
This section contains syntheses of enol esters and esters of unsaturated acids as well as ester molecules bearing a remote alkenyl unit. 1. 1.2 eq. LDA
2. 2 eq. HgC12
LizPdC14 THF-HMPA
25OC ,4d
Larock. R.C.; Stinn, D.E.; Kuo, M-Y.Tetrahedron Lett., 1990, 31, 17. 1. ACZO
OH 2. KHMDS SnBu3 t-BuMe2SiCi
/d
3. heat Ritter. K, Tetrahedron Lett., 1990, 31, 869.
63%
Ester - Alkene
Section 362
2. TMSCl
445
0 +
C12P
0 50)
(50 '
Pellon, P.; Himdi-Kabbab, S.; Rault, I.; Tonnard, F.; 1147.
*CHO
1. I-BuOK , THF -78°C , 0.5 M
Tetrahedron Lett., 1990, 31,
-OKoEt
2. CIC02Et
83% De Cusati, P.F.; Qlofson. R.A, Tetrahedron Lett., 1990, 31, 1405. CO (600 psi) NEt3, THF-MeCN
-
0
I 7 07
5% 100°C. Pd(PPh3)4 overnight w
%
Shimoyama, I.; Zhang, Y.; Wu,G.; &jgi&i& TetrahedronLett., 1990, 31, 2841.
OTs
p(=
1. Pd(dha)z/dppe THF , RT
CO Me 602Me
2. MeCH(C02Me)2) NaH
82% Stolle, A.; Salaun, J.; Tetrahedron Lett., 1990, 31, 4593. Stolle, A.; Salaun, J.; de Meijere, A. SynLetf, 1991, 321.
NaCo(C0)d. CHglz
€3-cic-€3 2.0"C. EDA, 8 h 3. HCI
* El E$to
Et
17%
Krafft.;Pankowski, J. TetrahedronLett., 1990. 31, 5139. Krafft. M.E,; Pankowski, J. SynLett, 1991, 865. NzC(C02Meh SbBu3, PhH
PhCHo
cat. CuI , 4 h , 7 F C
phYCo2Me
also works with ketones Liao, Y.; h n g . Y-7. TetrahedronLett., 1990. 31, 5897.
C02Me
98%
446
Section 362
Compendium of Organic Synthetic Methods, Vo18
+
1. t-BuOK , -3OoC, 14 h
0
C02Me
2. PhI , Pd(dba)z, 2 h 5% dppe
*
ph&
88% Fournet, G.; Balme, G.; Van Hemelryck, B.; Gore, I. Tetrahedron Lett., 1990, 31, 5147.
-
'7
.
MeOH ,CO RT 3%Pd@"hJ)p, 1 h
n-C6H
n-C,H,
- n-Cd-4
1
v
n-C,H13 C02Me
CO,Me
97%
(1:l E:Z)
Nokami. J,; Maihara, A.; l&jUTetrahedron Lett., 1990, 31, 5629.
-&c02et
,30%EtOH
[co2Et
CO,Et
bakers yeast, 48 h pH 7 . 2 , 37OC
74%
Co2Et
(endo:exo
0 100)
Rama Rao. K,; Srinivasan, T.N.; Bhanumalhi, N. Tetrahedron Lett., 1990, 31, 5959. C02Me MqSi S
C
a
M
e
Ph$+ BFd', MeCN RT.5h MeOzC
\
prepared from alkenes and 2-2-(silylethyl) dienes
Iiosomi.;Masunari, T.; Tominaga, Y.; Yanagi, T.; Hojo, M. Tetrahedron Letf., 1990, 31, 6201.
Me3Si-
csCT
1. iBuMpBr
Me
OH
cat. CpzTiClz
2. coz 3.H30'
c
Ito, T.; Okamoto, S.; &to. F, Tetrahedron Left., 1990, 3I, 6399.
62%
Crale.; Reader, J.C. Tetrahedron Letf.,1990, 31, 6585.
O
G Me 63%
54%
Ester - Alkene
Section 362
447
1. ClCOziBu 2. CH2Nz
.
A
Thijs, L.; Dommerholt, F.J.; Leemhuis, F.M.C.; Zwanenburp B, Tetrahedron Lett., 1990, 31, 6589.
H- C: C- C02Me
MesSnH ,THF
+Co2Me
2% Pd(PPh3)4 SnMe3 71% ~J.c.; Bronk, B.S.; Terrence, K.M.; Phillips, H.K. Tetrahedron Lett., 1990, 31, 6621.
CO2Me
1. LDA 2. Me1 3. mCPBA 4. TFA , CHC13
40%
Cow. R.M; Ritchie, B.M.; Shrier, A.M. Tetrahedron Lett., 1990, 31, 6789. C02Me
Pd(OAc)z, NEt3
Br
Br
MeCN ,100"C
I Tao, W.; Nesbitt, S.; fleck. R.S.J. Org. Chern., 1990. 55, 63.
C1
- j
C02Me CU", DMSO ,25"C
X c1 C02Me
5h
46%
C02Me
C?3t:ie1ci
Me02C
64% conversion
70% E isomer Tezuka. Y,;Hashimoto, A,; Ushizaka, K.;Imai. K. J. Org. Chem, 1990, 55, 329. 1. LiCHBr2 ; BuLi , TIPS-Cl P h e CHO
2.
n-C.jH1ICO2Et
TiC14, CH2C12
=
3. MeOH , -78"C+ RT Kowalski, C.J.; Sakdarat, S. J. Org. Chem., 1990, 55, 1977.
C02Me
n-C5H11'
Y P h 91%
448
Compendium of Organic Synthetic Methods, Vol8
CO$t
Section 362
1. LDA , THF , HMPA
-78°C
2. AcOH ,ether, -98°C
98%
Piers.;Gavai, A.V. J. Org. Chern., 1990, 55, 2374,
s ~ M ~ 0.1 , PdC12(MeCN)2 CH2C12 , RT , 18 h
bAc
c
Panek.;sparks, M.A. J. Org. Chem, 1990, 55, 5564. 1. sec-BSi ,TMEDA ,THF (inverse addition) , -78°C
d
NEt2
2. CuCN.2 LiCI , 0°C
-c
Sengupta, S . ; Sni&u,J
C1
-
J. Org. Chem., 2990, 55, 5680.
q i e
0
SiMe,
OAC 0
\
)L NEt,
Go
&Me
LDA , THF -78°C -+ RT
Me Me
Ph- CI C<
THF (0.05M) , 50°C
c
62%
Me
96%
0
Wender. P.A.; Manly, C.J. J. Am. Chem. Sac., 2990, 112, 8579. 0
71%
+.$
0
Ph
OMe
Brandvold, T.A.; Wulff.;Rheingold, A.L. .I. Atn. Chem. Soc., 1990, 112, 1645. 5% Pd(OAc), , ACOH acetone
cat. benzoquinone
D O A c AcO
85%
(83~17cktrans) Backvall. J-E.; Grandberg, K.L.; Hopkins, R.B. Acfa Chem. Scad., 1990, 44, 492.
73%
Ester - Alkene
Section 362
449
1. NaH 2. 5% PdZ(dba)3*CHC13
OAC 15% DMSO , 5 min
(4
1)
61%
Hanzawa, Y.;Ishizawa, S.; Ito, H.; Kobayashi, Y.; Bguchi. T,.I. Chem. Soc., Chem. Commun., 1990, 394.
+-$ 0
Bu3SnH , AIBN , PhH 5 mM , reflux, 48 h
Bu3Sn
34%
0
Baldwin.;Adlington, R.M.; Mitchell, M.B.; Robertson, J. J.
no lactone was formed
Commun., 1990, 1574.
1 . 0 3 , CHzC12, -78°C >
2. PhP=CHC02Me
Chem. Soc., Chem.
-C02Me 89%
H!m. Y-S.; Lu, L.; Li, S-Y. J. CO2Et
@02Et /
I
B
Chem. Soc., Chem. Commun., 1990, 1627.
u
c02et c02et
A ,DMF
5% Pd)OAc)z. Bu4NCl Na2CO3 , PPh3,60°C Id
Larock.;Fried, C.A. J. Am. Chem. Soc.. 1990, 112, 5882. l-BuSiMe2H. PhH M~
M>
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,,<
SePh
91%
Sakakibara, M.; Katsumata, K.; Watanabe, Y.; Toru, T.; Ueno. Y, SynLert, 1992, 965.
SECTION 364:
ETHER, EPOXIDE, THIOETHER SULFONATE XeF2(SPh)2 +
-SePh
CH2C12, -20°C
Unevama.; Kanai, M. Tetrahedron Lett., 2990, 31, 3583.
63%
- HALIDE, F
464
Compendium of Organic Synthetic Methods, Vsl 8
Section 364
GhMe, 110°C. 36 h
n-C7H1s'C02Me
OMe
Bunndle..;
2. Et2N-SF3, CH2CI2 55% McKinnis, B.R.; Narayanan, B.A. J. Org. Chern., 2990, 55, 768.
Fuchipaml.; Yamamoto, K.; Nakagawa, Y. .I. Org. Chetti., 2991, 56, 137.
via HOF*MeCN Hung, M.H.; Smart, B.E.; Feiring. A.E.; Rozen. S,.I. Org. Chertt., 2991, 56, 3187. CF3CHzO-Na+ , 1 10°C 10%CuBr , S d
PhOCH2CF3
7wo Rec. Trav. Chitii. Pays-Bas, 1991, 110, 299.
Keegstra, M.A.;
0
0
1. MeS-SMe2 BF4 , C H Q 2 2. NEt? , 3 HF ,0°C 3. aq. NH3
"'SMe
70%
Haufe. G.; Alvernhe, G.; Anker. D.; Iarent, A.; Saluzzo, C. .I. Org. Chern., 2992, 57, 714. Saluzzo, C.; Alvernhe, G.; Anker. D. Terruhedron Lerr., 2990, 31, 663. 0~~
Mn02-TMSCI
OMe
c1
Bellesia, F.; Boni, M.; Ghelfi.; Grandi, R.; Pagnoni, U.M.; Pinetti, A, Teirahedron, 1992,
48, 4519.
6
1 2 . MeCN
-20°C +RT
Or-BU
Marek.; Lefragois, J-M.; -1.
I
J -F. Terrahedron Lerr., 1992, 33, 1741.
94%
Ether - Ketone
Section 365
465
(37:63 cktrans)
U Ju& l;,?.
Gum, L.; Kim, S.W.; Kim,
Y.S.Tetrahedron Lett., 1992, 33, 3969.
SOC12, DMSO , RT -+ 70°C
SMe
,8t
Bellesia, F.; Boni, M.; Ghelfi.;Pagnoni, U.M.; Pinetti, A. Synlh. Cotnmun., 1992, 22, 1101.
SECTION 365: ETHER, EPOXIDE, THIOETHER Me
1.1 eq. HC(OEt)3, -78OC
OSiMe:,
1.2 eq. S n C 4 , 3 0 min
*
- KETONE
tLEt 88%
93:7 cistrans
Marlin, V.A.; Perron, F.; Alhizak K.F, Tetrahedron Lett., 1990, 31, 301.
-
0
4 O E t n - w1I
MeCN 20.C. 2 h
II-CSH1 1
Il-C-jH1 1 (3.1
Iqbal,- .J
n-C5H1 1
28%
1 ) 63%
aph
Tetrahedron kt~., 1990, 31, 1485.
KOPh,NEt3 C acetone
0
75%
OPh Hassner.;Naidorf-Meir, S.; Gottlieh, H.E. Tetrahedron Left.,1990, 31, 2181. +
j
PhSe
SiM% AgBF4, CH2ClzDCE , -5OOC -+ RT -
03
PhSe
Yamazaki. S.; Hama, M.; Yamahe, S. Terrahedron Lett., 1990, 31, 2917.
47%
466
Compendium of Organic Synthetic Methods, Vol8
25% overall
Paterson.;Osborne, S . Tetrahedron Lett., 1990, 31, 2213. MOMO
Me0
0
hv
Section 366
MOMO
OMOM
no yields Kraus. G.A, ; Thomas, P.J.; Schwinden, M.D. Tetrahedron Lett., 1990, 31, 1819.
84%
(70leman.;Grant,
E.B. Tetrahedron Lett. 1990, 31, 3677. e- , Pt anode, LiCIO4 CH2CI2, AQO
Me
1-2 mA/cm2
0 (p:o
Tetrahedron Lett., 1990, 31, 3933.
0:*
OH
.
PhCkCH ,NHEtz PdC12(dppf) 12OoC 20atmCO,2 h autoclave
=
56%
21:))
dph 81%
.. Kallnln.; Shostakovsky, M.V.; Ponomaryav, A.B. Tetrahedron Lett., 1990, 31,4073. PPhs , CC14, THF RT , overnight
78%
Arimoto, H.; Nishiyama, S.;
TefrahedronLett., 1990, 31, 5619.
Section 365
Ether - Ketone
467
3 NIS , 3 Li2CO3 16 MeOH , PhH e
hv (infrared lamp)
35°C
77% McDonald, C.E.; Holcomb, H.; Leathers, T.;Ampadu-Nyarko, F.; Frommer. J. Jr. Tetrahedron Lett., 1990, 31, 6283.
.
Ph-Pb(OAc)3
c o 2 i p r TMG THF , 3 d
OH
Ph
cat. Pd(OAc),, PPh3
0 71% TMG = N,N,N,N-ietramethylgu~idine Barton, D.H.R.; -v. D . U ; Finet, J-P.; Guiry, P.J.;Kielty, J.M. Tetrahedron Lett., 1990, 31, 6631.
ENo2 2 eq. PhSNa
78%
700C'3h
hl~~3-k; Kusama, Y . ; Oda, D. .I. Org. Chem., 1990, 55, 595.
1. MeOCH2CHN2,ether
NEt3
c1 2. Fthz(OAc)d Hudlickv. T,; Olivo, H.F.; Natchus, M.G.; Umpierrez, E.F.; Pandolfi, E.; Volonterio, C. J. Org. Chem., 1990, 55, 4767.
Et-CI C-Bu
PCWP , H202 CHC1-j. reflux
24h PCWP = peroxotungstophosphate* Ishii.;Sakata, Y . J. Org. Chent., 1990, 55, 5545. NaOCl , aq. MeCN , RT
OH
Foucaud. A,; le RouillB, E. Synthesis, 1990, 787.
q7% P
h
0
p C02Me
92%
468
Compendium of Organic Synthetic Methods, Vol8
Section 366
2 .THF
Me0
I.
Li-C3C
Crimmins. M.?'.; O'Mahony, R. .I. Org. Cheni., 1990, 55, 5894.
Ph
L
'Ph
PL = H
Itsuno.;Sakakura, M.; Ito, K. .I. Ph
wc1
Org. Chern., 1990.55, 6047. OSiMe,
. -78OC+ O°C * PhQ 2. NH4CI , H 2 0
1. Ph4CN
0
Ph
3. NE13.3 HF , 3 d 4. KOH ,ether, 15 h Marschner, C. Chem. Ber., 1990, 123, 107.
39%
m:
QPh
Phl(O1I)OTs , MeCN
Ph 75% * 0 0 Prakash.:Pahuja, S.; Goyal, S.; Sawhney, S.N.; Moriarty, R.M. SynLeu, 1990, 337. BFjeOEt? , CHzCI;! -78°C
(&&
82%
0
Kicci, A.; Derl'Innocenti. A,; Capperucci, A.; Faggi, C.; Seconi, G.; Favaretlo. L. SynLelt,
1990, 471.
Soderberg, B.C.: ;-
Sierra, M.A. J. Am. Chem. SOC., 1990, 112, 4364.
Section 365
Ether - Ketone
469
4'-Bu OSiMe3 , 5 % TMSOTf MeCN ,-4OOC. 30 min
OMe
*
92%
OMe 0
(92:8 anti:syn)
&ig~&; Kudo, K.; Hashimoto, Y.; Kimoto, H.; Hasegawa, M. Chetn. Left., 1990, 941.
SnBu3
Bu3SnH. AIBN , hv 0.8 h , 2OoC
* 62%
H . . Nlshlda.; Takahashi, H.; Takeda, H.; Takada, N.; Yonemitsu, 0. J. Atn. Chetn. Soc., 1990, 112, 902.
Co(acac)3, reflux, 150AcOH min
Ph
p+?-4h
c
Ph
0 Ph Me Nishino. H,; Yoshida, T.; Kurosawa K. Bull. Ckem. SOC..Ipn., 1991, 64, 1108. Me
.
10%
.
i TsOH ECHO
Me-OH Hopkins, M.H.; ;Rishton, G.M. .I. Atn. Chetn. Soc.. 1991, 113, 5354. Brown, M.J.; Harrison, T.; Herrinton, P.M.; Hopkins, M.H.; Hutchinson, K.D.; Mishra, P.; -.I. Am. Chetn. Soc., 1991, 113, 5365. OSiMe3
2eq.
PhS-
dph ,MeCN.RT 2 eq. CAN
0 t
ph+
75%
SPh
Narasaka, K.; Okauchi, T. Chetn. Letf., 1991, 515. 1 . BuzBOTf, iPr2NEt
phi
CH2C12, -78°C -+ O°C
2. PhSCl, -78°C
Paterson.;Oshome, S . SynLett, 1991. 145.
0
P h L S P h
"%
470
Section 366
Compendium of Organic Synthetic Methods, Vo18
Adam. W.; Hadjiarapoglou, L.; Smerz, A. Chent. Ber., 1991, 124, 227. 1. Meldrum'sacid&
.
Eid, C.N. Jr.;
8
>W% Tetrahedron Let(., 1991, 32, 461.
VO(OiPr)Cl2, N2 iPrOH-CH2C12 0°C (3 h); RT (5 h)
6
c1 (>98
67%
c2)
Hirao. T.; Mikami, S.; Mori, M.; Dhshiro, Y, Terruhedron Lett., 1991, 32, 1741. PhCH(OMe)2, Py TMSOTf , CH2C12
-78°C
RT
p:e Q0 91%
Kim. S.; Kim, Y.G.; Park,J.H. Tetrahedron Let(., 1991, 32, 2043. O'IUSOTMS
Ad
OMe
TMSOTf
0
C0,Me
Me
56%
MoIander. G.A,; Cameron, K.O. .1. 5rg. Chem., 1991, 56, 2617. ELOH, I-120, RT
SOzPh EtO+
0 also reacts with other nucleophiles
Weichert, A.; Hoffmann. H.M.R,.I. Org. Chem., 1991, 54, 4098.
0
90%
Ether - Ketone
Section 365
d OH
47 1
1 . 3 eq. LDA , TMSCl
TEA 2. TiC14, BnCHO 3. H2S04, AcOH
&ph 78%
also reacts with TiClhetones
Kellv. S.E.; Vanderplas, B.C. .I. Org. Chem., 1991, 56, 1325. PhSeSePh , MeOH (NH4)2S208 , 1.5 h
Me0 OMe
30%
Tiecco.;Testaferri, L.; CO.
Bartoli, D.; Marini, F. J. Org. Chem., 1991, 56, 5207. M.; Testaferri, L.; Tiopoli. K; Bartoli, D. .I. Org. Chem., 1990, 55, 4523.
Pirruae. Mac,; Zhang, J.; McPhail, A.T. J. Org. Chem., 1991, 56, 6269.
Pirrune. M.C.; Zhang, J. Tetrahedron Lert., 1992, 33, 5987.
Genicot, C.; Gobeaux, B. Ghosez. L Tetrahedron Lett., 1991, 32, 3821.
0 Bn,N/ Me'
Me
f-BuOOH ,f-BuOK 'MFlNH3
Me& NBn,
Me
+
(95
;-
Lauterbach, E.H. Tetrahedron Lert., 1991, 32,4477.
Singh, O.V.;
Kanil.;Gag, C.P.; Kapoor, R.P. Terrahedron Lett.,
M e e o M e NBn, 5)
65%
1991, 32, 5619.
472
Compendium of Organic Synthetic Methods, Vo18
Section 366
R = Me 8 6 % 0 R = iBu 72% Tetrahedron Lett., 1991, 32, 5465.
B a r , K.J.; Watson, B.T.;
0.1 MeAlC12 , 2 h
Me
-6S"C
-
JPo Me
69%
(31:69 dr)
Rogers, C.; m v . B.G Tetrahedron Lett.. 1991, 32, 6477.
Kobbing, S.; Maitav. J. Tetrahedron Lett., 1992, 33, 927.
="u-
SiMe,
'"G
SnC14
+=( SePh
Me$i
66%
Yamazaki. S.; Fujitsuka, H.; Yamabe, S.; Tamura, H. J. Org. Chem., 1992, 57, 5610. PhCHO , THF ,60T Mey-0 c1
Bu3Sn-N(Et)C02Me +
M e G 0 P h 59% (1387 &:trans)
Yamasaki, H.; Baba, A.; Matsuda, H. .I. Org. Chern., 2992, 57, 6909. Shibaca.; Yamasaki, H.; Baba, A.; Matsuda, H. SynLeit. 1990, 490.
(24
Spero, D.M.;
Tetrahedron Lett., 1992, 33, 1143.
b
o
T
413
Ether - Ketone
Section 365
C
O
,
M
e
0
*&
.
1. MsNj NEt3, MeCN , 2 5 T
2.
a&p.2';.,
C02Me
RhdHCWz
(
54%
Ye, T.; McCann.; Murphy, E.; Doyle, M.P. Tetrahedron
McCarthy, ;N.; . A .MLett., 1992, 33, 5983.
B
OSiMe,
bSPh
CH2C12,O"C , 3 0 rnin N-TS
Ph-
s.y.SPh
75%
Ts
Maonus. P,; Rigollier, P. Tetrahedron Lett., 1992, 33, 61 11.
hv , PhH , reflux
96%
0Chen, C.; Crich. D.; Papadatos, A. J. Am. Chem. SOC., 1992, 114, 8313.
0
0
ph
1. TMSOTf , EtN(iPr)2 CH2C12 2. MgBryOEt2
L
S
P
h 90%
Kosugi. H,; Hoshino, K.; Uda, H. .I. Chem. SOC., Chem. Commun., 1992, 560. TMSOTf , PhMe
PhS (97
3)
62%
Kudo, K.; Saieo. K.; Hashimoto, Y.: Saito. K.; Hasegawa, M. Chem. LRtt., 1992, 1449. 1. PhCHO , SnCl2 2. EtOH
OAc
3.NCS,CHzC12
*
phYY 84% EtO 0
m; Kobayashi, Y.; Yanagi, R.; Kurusu, Y. Chem. Lett., 1992, 2039.
474
Section 366
Compendium of Organic Synthetic Methods, Vo18
SECTION 366: ETHER, EPOXIDE, THIOETHER
Br
- NITRILE
Br
41%
8%
Baldwln.;ONeil, LA. Tetrahedron Left., 1990, 31, 2047.
C
1. Ph3C-CkN-O , PhH 25°C
I
2.12, CH2C12
(1:4 cis:trans)
Kurth.; Rodriguez, M.J.; Olmstead, M.M. J. Org. Chem., 1990, 55, 283. TMS-CN ,CoC12
Ph+OEt OEt
*
CHzC12 Soga, T.; Takenoshita, H.; Yamada, M.; Muk&uuJ 3122.
&cHo
CICHzCN ,aq. NaOH Et3BnNCI ,20°C,
Ph
98%
Bull. Chem. SOC. Jpn., 1990, 63,
6-1.. Me
77%
m n d a m . Y.S, ; Leelavati, P. .I. Id.Chem. Soc., 1990, 67, 253.
c1
n-C9H
i$- SPh
MejSiCN , SnCI4 CH2C12
Fortes.;Okino, E.A. Synth. Commun..
t
68%
1990, 20, 1943.
:-AIEt2 ,ZnC12
OMe
E~~&LH.H.; Yamanaka, T.; Yakuma, K.; Miyazaki, M.; KitaY.. Chem Soc., Chem. Commun., 1991, 533.
Ether - Alkene
Section 367
475
SECTION 367: ETHER, EPOXIDE, THIOETHER
- ALKENE
Enol ethers are found in this section as well as alkenyl ethers.
reflux
0 Geng, L.; !,&ATetrahedron , Lett., 1990, 31, 111.
Me
65%
-x
Bu3SnLi. THF 0°C ,20 min
CI
Ph
Ph
98%
Fujiwara, S.; Katsumura.; Isoe. S . Tetrahedron Lett., 2990, 31, 691.
6
1, M e h S i L i 2.n-BuLi. THF
OSiMezPh
* &Me
3.MeI
Brook reanangement
40%
Koreeda.; Koo, S. Tetrahedron Lett., 1990, 31, 831.
Me02C
0
EtO
NPhth
NPhth
(1
1.3) 91%
230 h
Tietze.;Hartfiel, U. Tetrahedron Lett., 1990, 31, 1697. OSiMe3
SiMe3
TMSOTf
t
OMe
&
75%
Lee. T.V,; Roden, F.S.; Yeoh, H.T-L. Tetrahedron Lett., 1990, 31, 2063.
Ph- ci
'-
B(SeMeb ,RT CH2CI;!,30 mine
Ph
Phy
MeSe)=
61%
i-
MeSe
SeMe 18%
Kataoka, T.; Yoshirnatsu, M.; Shirnizu, H.; Hori. M. Tetrahedron Lett., 1990, 31, 5927.
476
Compendium of Organic Synthetic Methods, Vol8
Section 367
Saiuzzo, C.; Alvemhe, G.; linker. D, Tetrahedron Letf.,1990, 31, 2127.
9
C02Et
es- 103"C,5d
2-
0
+
C0,B
OTBS
50%
1)
(7.3
Block.;Zhao, S.H. Tetrahedron Lett., 1990, 31, 5003.
OTBS
TBS = SiMqf-Bu
Friesen. R.W.; Siurino, C.F. .I. Org. Chem., 1990, 55, 2572.
.r-Bu
Revis.;Hilty, T.K.J. Org.
80%
Chem., 1990, 55, 2972.
5% P ~ ( O A C NaOAc )~, 100°C , PPh3 ,BusNCl
68%
Larock. R.C,; Berrios-PeAa, N.; Narayanan, K. J. Org. Chem, 1990, 55, 3447. n-C7H15
Me<
0
cT'ie
RhCI(PPh3h , MeCN 90°C , 15 min
n-C7HI5
4
also with allenic aldehydes
Marshall.: Robinson, ED. .I. Org. Chem., 1990, 55, 3450.
Me
Me 80%
Ether - Alkene
Section 367
477
* Q
O A ~ CC14, 135°C , 12 h
Me3S i
OAc
Me3S i
94%
Clark, D.L.; Chou, W-N.; White. J,B,.I. Org. Chem., 1990, 55, 3975. Chou, W-N.; White. J.& Tetrahedron Lett., 1991, 32, 157.
00
1. LiHMDS , THF-HMPA
2. PhN(SOEF3)2 3. BuzCuLi
Tsushima, K.: Mural.A. . Chem. Left., 1990, 761.
w;Hashimoto, Y.; Kihara, N.; Hara, K.; Hasegawa, M. Chetti. Lett., 1990, 1097. n
s s
x Ph Me
T d h , CH2CIz. RT
n
Ms
S
t
58%
Me
Ph
Tani. H.; Inamasu, T.; Tamura, R.; Suzuki, H. Chetti. Lett., 1990, 1323.
\/\/\\ SnCI4, CH2C12, .O"C3 h
Me@C
q:
* A Me02C
63%
0 '%b
Sera.;Ohara, M.; Yamada, H.; Egashira, E.; Ueda, N.; Setsune, J. Chetn. Letf., 1990, 2043.
0
TiCb ,Zn
dioxane ,reflux
;
55%
Me
Me
Nagak, S.K. J. Chetn. SOC.,Chetn. Cotnmun., 1990, 150. AIzO3, PhOII
Me02C- Cr C- C02Me
c
PhO
)-7
Me02C
COzMe
91%
Kodoman.; Sakamoto, T.; Yoshitorni, S. .I. Chetti. SOC., Chetti. Comntun., 1990, 701.
47 8
Compendium of Organic Synthetic Methods, Vol8
Section 367
Me I
Arya, P.;Chan. T - a J. Chem. SOC., Chem. Commun., 1990, 967.
0
0
rTe(iBu);, Br
PhCHO
=/
Ph<
-t
KOH(solid) RT78 h THF (trace water)
n 96%
t
Zhou, Z-L.; Sun, Y-S.;
m
a::
Bi. L-L.: H u n g . Y - Z , J . Chem. Soc,, Chem. Commun., 1990, 1439. 2 eq. EtSH , 12 h cyclohexane
0 Me
(70:30 cktrans)
c1
c,
-5"CjRT
Me
75-88%
v . I.G.; Ramazanov, G.A.; Keriomov, F.F.; Abbasov, I.M.; Zefirov. N.S. Zhur. Org. Khim., 1990, 26, 1638 (Engl., p. 1416). 2,6-di-f-butylpyridine 2 eq. SnC14, -10°C
L O
300 min 13%
25%
Blumenkopf, T.A.; Bratz, M.; Casmeda, A.; Look, G.C.; Overman.;Rodriguez, D.; Thompson, A S . J. Am. Chem. SOC.,1990, 112, 4386. Cp2TiMe2 , PhMe ,65"C
*
eph
a
41%
Petasis. N.A,; Bzowej, E.I. J. Am. Chem. SOC., 1990, 112, 6392. 1. (Se), ,90°C
2 Ph,P=CHPh 2.
H
* Ph
34%
Okuma.;Komiya, Y.; Kaneko, I. ; Tachibana, Y.; Iwata, E.; Ohta, 11. Bull. Chem. SOC. Jpn., 1990, 63, 1653.
Ether - Alkene
Section 367
MeS
1
0
Ph
Bu3SnH. BEt,
- \ = \ SPh
Ph%
SPh SPh Nozaki, K.; Oshima.,
479
70%
(92:8 E:Z)
Bull. Chem. SOC. Jpn., 1990, 63, 2578.
Mesu
1. BuLi , HMPA 2. Me1
*
SiMe,
70%
(66:34 E:Z)
Miura, K.; Qshima. K.; Utimoto. K*Eull. Chem. SOC.Jpn., 1990, 63, 2584. Na ,CISiMe3 ,THF ,0°C 105 min .)))))>)
Fadel, A,; Canet, J-L.; Blaiin.
0~~
t
J.SynLert, 1990, 89.
00SiMe3 83% OSiMe,
ui
1. PPhJ , TMSOTf ,THF , -3OOC 2. BuLi ,THF ,-78OC Ph
d o M e 4.3.BnBr KOH ,MeOH Kim.; Kim, Y.C. SynLett, 1990, 115. 1. BuLi 2. BuI , THF ,HMF’T 3. r-BuOK. THF. refluxC
t-Buo-
71%
Or-Bu 67% (21:79 E:Z)
Julia.;Uguen, D.; Verpeaux, J-N.; Zhang, Ph0zSbS02Ph
D. S y n k f t , 1991, 505.
1. LDA ; Me1 2, BLSiMe,
*
Et2AlCIz , C H E 5
Me
38%
SimDkins. N.S. Tetrahedron, 1991, 47, 323.
0 Me Jj&&J,;
n-GH11
‘OZMe
Co(OAc)l, 0 2
Bhatia, B.; Nayyar, N.K. Tetrahedron. 1991, 47,6457.
58%
Compendium of Organic Synthetic Methods, Vol8
480
BuzSn(OT92, DCE BuzSn(SPh)z, 35°C
-OMe OMe
Section 367
/
PhSL s p h
12h
71%
(72:28 E:Z) Sam, T.; Otera.; Nozaki,H. SynLert, 1991, 903.
1. PhCHO , PhSH , TsOH 2. BuLi
Ph
-
3. MeCH2X SPh H 4. BF3 Afridi, AS.; Kuzmierkiewicz, W. Helv. C h k . Acta, 1991, 74, 1931.
;-
1 . EtCu(CN)ZnEt-2 LiCl 0°C , 1 h 2.
Bu- C5 C- SMe
Bu
Br
6
e:M OMe
OMe e- (RVC anode)
LiClO4, CI12C12
20%CD30D
92%
SMe
J. Am, Cheni. Soc.. 1991, 113, 5735.
Rao, S.A.;
92%
*
SiMe,
-I60%
10%
OMe
Ifudson, C.M.; Marzabadi, M.R.; Moeller. KD-;New, D.G. 1. Am. Chem. Soc., 1991, 113, 7372.
*s-~ Pi01
0 V M c ~ B ~ -78°C -+ RT
\
+
85%
u; Maezaki, N.; Kurumada, T.; Fukuyama, 11.; Sugiyama, K.; Imanishi, T. J. Cheni. W O
SOC.,Chem. Commun., 1991, 1408.
Me&
-ue3 10%Et3A1, CHzClz 15"C, 20 h
Fujiwara, T.; Suda, A.;
Cheni. Lett.. 1992, 1619.
82%
Ether - Alkene
Section 367
F:::
C S 2 , 2 eq. Me1 ,MeCN KF , A1203 , RT
58%
Villemin. D,; Ben Alloum, A. Synthesis, 1991, 301.
Tmst.B M ; Tometzki, G.B. Synthesis,
48 1
1991, 1235.
*
SnBu3 7 CH2C12
t
t-B uMe2SiOTf
82%
Kim., Lee, J.M. Synth.
Cornntun., 1991, 21, 25.
Me0
MeOv
1. MejSi-Jl,,SPh Tic14
)7-Br2. (Bu3Sn)z. Phli hv , 10°C
Me0
33%
95%for step 1; 35% for step 2
Ward.; Kaller, B.F. Tetrahedron Lett., 1991. 32, 843.
OMe
, -30°C
CH2C12,48 h Me02C-CHO
c
“‘CO ,Me (78
(94%ee)
Terada, M.; Mlkami.; N&iJ.
Tetmhedron Lett., 1991. 32, 935.
(9
Koerber, K.; Gore, J.; Vatele, J-M. Tetrahedron Lett., 1991, 32, 1187.
22) 77% (990% ee)
91)
72%
482
Compendium of Organic Synthetic Methods, Vol8
AIiquat 366,O"C do]2%THF, t-BuOK ,2h
Br
0
Bailey, W.J.; Zhou. L-I,Tetrahedron Lett., 1991, 32, 1539.
]I+
68%
PhSCl
Me
-
SiMe3
Ph
Section 367
P
h b SPh 72%
(90% de) Nativi, C.; Palio, G.; Taddei. M, Tetrahedron Lett., 1991, 32, 1583.
iM;
DMUPhH ,Zncl2
microwavcs (600 w)
CH(OMe),
Me
~
5min
Me
"CH(OMe),
with no microwaves. at 140°C, 0%yield
CH(OMe),
Me
82%
Stambouli, A.; Chasuette, M.; Soufiaoui, M. Tetrahedron Lett., 1991, 32, 1723.
NaH ,THF
*
Me0
SiMe, 95%
Pegram, J.J.; Anderson, C.B. Tetrahedron Lett., 1991, 32, 2197.
du
0.2 eq. AgNO3 ,H20 CaCO3 , acetone, RT c
Me '
Me
0
COzMe 95%
0"'"
Marshall.: Wang, X . J. Org. Chem., 1991, 56, 960. Li2CO3 ,acetone-AcOH
2 eqp-benzoquinone 5% Pd(OAc)z, 20°C
c
Aco"'
Backvall. J-E,; Anderson, P.G. J. 5rg. Chem., 1991, 56, 2274.
(>98%Irans)
86%
Ether - Alkene
Section 367
AgOS02To1, MeCN PhSeCl , RT
Ph- CZ C-Me
-
483
To102so>-<”” Ph SePh
75%
Back.;Muralidharan, K.R. J. Org. Chem, 1991, 56, 2781.
Back.:Muralidharan, K.R. Tetrahedron Lett., 1990, 31, 1957.
PhCHO
1. IZn(CN)Cu(CH2)-ZnI THF , -60°C -+ -25°C
2. I2 , -70°C + RT
c
59%
Ph
Hudlickv. T,; Barbieri, G. J. Org. Chem., 1991, 56, 4598. 1. MeLi 2. PhMezSiCl
OSiMe3
L O S i M e 2 P h
93% Duhamel. L,; Guillemont, J.; Poirier, J-M.; Chabardes, P. Tetrahedron Lett., 1991, 32, 4495, 4499. 1. SnC14
2. Ph-OMe , MS 4A
SnBu3 OMe
Takeda.,Kanamori, F.; Masuda, M.; Fujiwara, T. Tetrahedron Lett., 1991, 32,5567. Takeda.:Kanamori, F.; Matsusita, H.; Fujiwara, T. Tetrahedron Lett., 1991, 32, 6563 [with NBS; AIC131.
r-Bu02C- C: C. C02r-Bu
Me
OH
K2CO3 , acetone, 80°C 20 h
c
MenC02t-B~ OH Me”
0
C02t-Bu 88%
Jauch. J,; Schurig, V. Tetrahedron Lett., 1991, 32, 4687.
PhS- Cr C-Me
Pd(PPh&, PhH Bu3SnH
Mapriotis. P.A,; Brown, J.T.; Scott, M.E. Tetrahedron Lett., 1991, 32, 5041.
484
Compendium of Organic Synthetic Methods, Vo18
Section 367
1 . 2 eq. 1-BuLi , ether 2. allylmagnesium bromide 3. ZnBq 4. aq. HCI
Ot-Bu 81%
(955 dr) Marek. L;Lefrancois, J-M.; F Tetrahedron Lett., 1991. 32, 5969. Marek, I.; Normant, J.F. Terrahedron Lett.. 1991, 32, 5973. Marek.; Alexakis, A.; Normant. J-F, Tetrahedron Lett., 1991, 32, 6337. (95%yield)
H- Ci C-(
OEt
OEt
1. BusSnCu(Bu)CNLiz THF , -78'C, 2 h *
2.H20
Bu3sn-roEt OEt
Beaudet, I.; Parrain, J-L.; Quintard. J -P, Tetrahedron Lett., 1991, 32, 6333.
(92
\
c1
/
96%
RT Telrah.edronLett., 1991, 32, 6633.
Balasubramanian, T.;
p h y c l
p-TsOH,PhH
8)
1. (Bu3Sn)zSe 2. TBAF.3 H 2 0 , THF
3.
4
Q
Ph
7990
(5941 endo:exo)
SePi.;Kato, M.; Nakajima, T.Tetrahedron Lett., 1991, 32, 7427. Ph- Cr C-H
PhSeSePh , neat hv (sunlighVpyrex)
c
PhSe PhhSePh
83%
(82:18 E:Z) Ocawa. A; Yokoyama, H.; Yokoyama, K.; Masawaki, T.; Kambe, N.; Sonoda. N, .I. Org. Chem., 1991, 56, 5721. Qgawa. A,; Obayashi, R.; Sekiguchi, M.; Masawaki, T.; Kambe, N.; Sonoda. N, Terrahedron Lett., 1992, 33, 1329.
Ether - Alkene
Section 367
Ph2CHCI
Ph
S 8 , DBU , MeCN
25°C
+
485
60%
Abelman. M.M. Tetrahedron Lett., 1991, 32, 7390, n-C6H I
gz C>
5% PdCIz(MeCN)2
Me MeCN-H2O , 2 h
flMe
4
0
n-C6Hl3 0 76% Fukuda, Y.; Shiragami, H.; Utimoto. K,; Nozaki, H. J . Org. Cherrz.. 1991, 56, 5816. Kataoka, Y.; Tezuka, M.; Takai. K,; 1Jtimoto. K, Tetrahedron, 1992, 48, 3495.
Phqo OMe
reflux
Cp2TiBn2, PhMe 55°C
Ph b
Ph
Me0
84% (1436 E:Z)
N . G ; Bzowej, E.I. .I. Org. Chein., 1992, 57, 1327. n-CrjH,,CHO, CCb
Me3Si0
-
83%
cat. TMS-OTf, PrOTMS
20oc 0 ?l-C6H13 M a k L J J L Mekhalfia, A.; Bayston, D.J.; Adams, H. J. Org. Chern., 1992, 57, 221 1 .
Mekhalfia, A.; Markb, I.E.; Adams, H. Tetrahedron Lett., 1991, 32, 4783.
UH
2
(1
8)
72%
Luo. F-T,; Schreuder, 1.; Wang, R-T. .I. Org. Chem., 1992, 57, 2213.
Ph
>cs CJ
Bu
PhI ,CO , PhH-NEt3 PdCI2(PPh,),
Ph
Ph
0
0
Bu
65%
Okuro, K.; Furuune, M.; Miura. M,; Nomura, M. J. Org. Chem., 1992, 57, 4754.
Br
NaOMe , 10%CuBr 85°C. NMP , 1 h
m.M.A. Tetrahedron. 1992, 48, 2681.
70%
486
Compendium of Organic Synthetic Methods, Vol8
d
o
o
o+
Section 367
Ti-graphite ,THF reflux, 8 h
88%
Ph
Furstner.;Jumbam, D.N. Tetrahedron, 1992,48, 5991. Furstner.
; Jumbam, D.N.; Weidmann, H. Tetrahedron Letf., 1991, 32,6695.
Mc
I-BuOK
Br
Aben, R.W.M.; Scheeren. J.W. Rec. Trav. Chim. Pays-Bas, 1992, 109, 399.
Fe(acac)3/2,2'- bipy A1Et-j 3.
OSiMeat-Bu
Takacs.;Myoung, Y.C. Tetrahedron Letf., 1992, 33, 317.
JSnBu3
Ph- , 0
AcCl, CH2Cl2
c
7
(E + Z)
PhS
"goodyield"
OSiMe,t-Bu
JL OAc
50%
Beddoes, R.L.; MacLeod, D.; Moorcroft, D.; (hale. P,; Zhao, Y. Tetrahedron Lert.. 1992, 33,
417.
alan. A.S,; Prieto, R.; Mueller, B.; Peters, D. Tetrahedron Lett., 1992, 33, 1679.
y)@
Me0
1. Co(1) salophen , THF 2. hv (sunlamp) F
Me0
&s88(
Me
Ali, A.; Ilarrowvcn, D.C.; Pattenden. G, Tetrahedron Lett., 1992, 33, 2851.
Me
43%
Ether - Alkene
Section 367
n-C5HI,-CI C-0 "
Q
487
-.,,,Q
n - w ,i
LiAIH4, THF
Ph Ph Sob, L.; Castro, J.; Movano.;I?&&J ;U Riera. A. Tetrahedron Lett., 1992, 33, 2863.
Br ,
" . k qOAc
y)
Br
K2CO3, MeOH 10 min
*
0
99%
0
Grandjean, D.; pale. P.; Chuche, J. Tetrahedron Letr., 1992, 33, 4905. BuLi , THF
Jin, F.; Jiang, B.; XILY.Tetrahedron Left., 1992, 33, 1221.
OSi(iPr),
95%
Bn
OH SMe
n-C&II3CHO
OSi(iPr),
1.2 eq. MezAICI
94%
"a oooPh
(85: 15 threo:erythro , 83% ee) Tanino, K.; Shoda, H.; Nakamura, T.; JCuwaiima. I , Tetruhedron Lett., 1992, 33, 1337.
0 0
'
Pd(OAc)Z, (R)-BINAP PhH , PhOTf , 9 d
c
0
l!&ph
quant.
(71
29)
(>96%ee)
(17% ee)
Ozawa. F: Kubo, A.; Havashi. T, Tetrahedron Lett., 1992, 33, 1485.
9
EtO-P~ ~ 0 CH3'
1 . 3 eq. LDA ,THF , -78OC 2 . 2 eq. PhSeBr ,60°C
c
3.PhCH0,RT
Ph
*
Shin, W.S.; Lee, K.; Oh. D.Y.Tetrahedron Lett., 1992, 33, 5375.
-
BuCH(0Me)Z. CHF12 TMSOTf, -78°C
SePh SePh
97%
Ma
SiMe3 Bu Hojo, M.;Ohsumi, K.;Hosomi. A, Tefruhedron Lett., 1992, 33, 5981.
85%
Compendium of Organic Synthetic Methods, Volt?
488
1. PhSeBr , THF , -78°C
2.H30’
Et
SePh
Et Tetrahedron Lett., 1992. 33, 5097.
Chung, H.S.;
,EtOH NEt9CaC12
Section 367
71%
Et
so+ 65%
pjnto. I.Lk;Buckle, D.R.; Rami, H.K.; Smich, D.G. Tetrahedron Len., 1992, 33, 7597. 1. BuLi ,THF ,-78°C. 1-BuOK ; BuLi
2 . M e e C H 0
Wang, W-B.; floskam-
*
TBSO
0
TBSO
3. S i 0 2 M 2 0 , microwaves 5 min 4. TBSCl , imidazole , DMF
(1
75%
1)
Tetrahedron Lett., 1992, 33, 7631. > 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
