Annual Reports in Organic Synthesis, Volume 2004 (Annual Reports in Organic Synthesis)

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Author: Philip M. Weintraub | Kenneth Turnbull | Jeffrey Sabol | Peter Norris

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annual reports in organic synthesis - 2004

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annual reports in organic synthesis - 2004 Philip M. Weintraub

Kenneth Turnbull

Aventis Pharmaceuticals Bridgewater, New Jersey

Wright State University Dayton, Ohio

Jeffrey Sabol

Peter Norris

Aventis Pharmaceuticals Bridgewater, New Jersey

Youngstown State University Youngstown, Ohio

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Contents PREFACE .................................................................................................... LIST OF JOURNALS ABSTRACTED ...................................................... GLOSSARY OF ABBREVIATIONS ....................................................... I

xi xv xvii

CARBON-CARBON BOND FORMING REACTIONS A Carbon-Carbon Single Bonds (see also: I.E., I.F., I.G., I.H.) ........1 1 Alkylations of Aldehydes. Ketones. and their Derivatives .......1 2 Alkylations of Nitriles. Acids and Acid Derivatives ................2 3 Alkylations of p-Dicarbonyl. p-Cyanocarbonyl Systems. and Other Active Methylene Compounds ................................ 5 4 Alkylations O f N.. P.. S.. Se & Similar Stabilized Carbanions ....7 5 Alkylations of Organometallic and Related Reagents (see also: I.B.3., I.B.4., I.F., I.G.) .............................................. 9 6 Other Alkylation Procedures .................................................. 12 7 Nucleophilic Addition to Electrophilic Carbon ...................... 12 a 1.2.Additions .................................................................... 12 ( 1 ) Aldol-Type 1. 2 Additions .......................................... 12 (2) Add’n of N. P. S. Se & Similar Stabilized Carbanions ..19 (3) Addition of Organometallic and Related Species ......20 (4) Other 1 2-Additions .................................................... 31 b Conjugate Additions ......................................................... 33 (1) Enolate-Type Carbanions ........................................ 33 35 (2) Organometallic and Related Reagents ..................... (3) Other Conjugate Additions ...................................... 38 8 Other Carbon-Carbon Single Bond Forming Reactions .........40 B Carbon-Carbon Double Bonds (See also: I.E.l) ........................... 43 1 Wittig-Type Olefination Reactions ......................................... 43 2 Eliminations ............................................................................ 45 45 a Alcohols and Derivatives .................................................. b Halides .............................................................................. 46 c Other Eliminations ............................................................ 46 47 3 Olefin Metathesis .................................................................... 4 Other Carbon-Carbon Double Bond Forming Reactions .......50 5 Vinylations.............................................................................. 53 6 Allene Forming Reactions ...................................................... 5 5 C Carbon-Carbon Triple Bonds ....................................................... 57 D Cyclopropanations ........................................................................ 60 1 Carbene or Carbenoid Additions to a Multiple Bond .............60 2 Other Cyclopropanations ........................................................ 62 E Thermal and Photochemical Reactions ........................................ 64 1 Cycloadditions ........................................................................ 64 2 Other Thermal Reactions ........................................................ 72

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CONTENTS

3 Photochemical Reactions ........................................................ 73 F Aromatic Substitutions Forming a New Carbon-Carbon Bond ....75 1 Friedel-Crafts Type Aromatic Substitution Reactions ...........75 2 Coupling Reactions to Form an Aromatic-Aromatic Bond ....78 3 Other Aromatic Substitutions and Preparations ..................... 82 G Synthesis via Organometallics ...................................................... 86 1 Synthesis via Organoboranes .................................................. 86 2 Carbonylation Reactions ......................................................... 88 3 Other Syntheses via Organometallics ..................................... 91 H Rearrangements ............................................................................ 95 1 Claisen. Cope and Similar Processes ...................................... 95 98 2 Other Rearrangements ............................................................ OXIDATIONS 102 A C-0 Oxidations .......................................................................... 1 Alcohol + Ketone. Aldehyde .............................................. 102 2 Alcohol. Aldehydes -+ Acids. Esters ................................... 104 B C-H Oxidations........................................................................... 105 1 C-H -+ C - 0 .......................................................................... 105 2 C-H + C-Hal ........................................................................ 107 C C-N Oxidations........................................................................... 107 D Amine Oxidations ....................................................................... 108 E Sulfur Oxidations ........................................................................ 109 F Oxidative Additions to C-C Multiple Bonds .............................. 110 1 Epoxidations ......................................................................... 110 2 Hydroxylations ..................................................................... 113 3 Other Oxidative Additions to C-C Multiple Bonds ..............114 G Phenol-Quinone Oxidation ......................................................... 115 H Dehydrogenation ......................................................................... 115 I Other Oxidations ........................................................................ 116 REDUCTIONS A C=O Reductions (see also 1II.F.1) .............................................. 118 1 Aldehydes, Ketones + Alcolols ........................................... 118 2 Acids. Esters, Amides + Aldehydes .................................... 120 3 Acids. Ester. Amides -+ Alcohols ........................................ 120 B C-N Multiple Bond Reductions .................................................. 121 1 Imine Reductions .................................................................. 121 123 2 Reductions of Heterocycles .................................................. C Reduction of Sulfur Compounds ................................................ 123 D N - 0 Reductions .......................................................................... 124 E C-C Multiple Bond Reductions .................................................. 125 1 C=C Reductions .................................................................... 125 2 C=C Reductions .................................................................... 127 F Hetero Bond Reductions ............................................................. 128

CONTENTS

IV

V

VI

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128 1 C-0 -+ C-H .......................................................................... 2 C-Hal -+ C-H ........................................................................ 129 130 3 C-S + C-H ........................................................................... G Reductive Cleavages................................................................... 130 1 Oxiranes ................................................................................ 130 131 2 N-0 Cleavages ................................................................... 132 3 Other Reductive Cleavages................................................... H Reduction of Azides ................................................................... 132 I Other Reductions ........................................................................ 132 SYNTHESIS OF HETEROCYCLES A Oxiranes, Aziridines. and Thiiranes ........................................... 133 B Oxetanes. Azetidines. and Thietanes .......................................... 137 C Lactams ....................................................................................... 137 D Lactones ...................................................................................... 146 E Furans and Thiophenes ............................................................... 151 F Pyrroles. Indoles. etc ................................................................... 159 G Pyridines. Quinolines. etc ........................................................... 167 H Pyrans. Pyrones. and Sulfur Analogues ...................................... 174 I Other Heterocycles with One Heteroatom .................................. 179 J Heterocycles with a Bridgehead Heteroatom ............................. 180 K Heterocycles with Two or More Heteroatoms............................ 183 1 Heterocycles with 2 N’s ........................................................ 183 a 5-Membered.................................................................... 183 b 6-Membered.................................................................... 188 c 7-Membered.................................................................... 191 2 Heterocycles with 2 0’s or 2 S’s .......................................... 192 3 Heterocycles with 1 N and 1 0 ............................................. 193 199 4 Heterocycles with 1 N and 1 S ............................................. 5 Heterocycles with 1 0 and 1 S ............................................. 202 6 Heterocycles with 3 or more N’s .......................................... 203 7 Heterocycles with 2 N’s and 1 0 .......................................... 206 8 Heterocycles with 2 N’s and 1 S or 1 Se .............................. 206 L Other Heterocyles ....................................................................... 207 M . Reviews ....................................................................................... 209 PROTECTING GROUPS .................................................................. A Aldehyde and Ketone Protecting Groups ................................... 215 B Amino Acid Protection ............................................................... 217 C Amine Protecting Groups ........................................................... 217 D Carboxyl Protecting Groups ...................................................... 220 E Hydroxyl Protecting Groups ....................................................... 221 F Other Protecting Groups ............................................................. 224 USEFUL SYNTHETIC PREPARATIONS A Functional Group Preparations ................................................... 225 I Acetals and Ketals ............................................................... 225

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2 Acids and Anhydrides (see also: I.A.2, II.B.l, V.E) ............228 3 Alcohols& Related Species (see also: II.B.1, III.A., V.E., VI.A.ll) ...229 4 Aldehydes and Ketones (see also: I.A.l., I.G.2., II.A.l .......231 5 Amides and Related Species................................................ 233 6 Amines ................................................................................ 237 241 7 Amino Acid Derivatives ...................................................... 8 Azides .................................................................................. 246 9 Carbohydrates ...................................................................... 246 10 Esters (see also: I.G.2., IV.D., V.D., VI.A.3) ...................... 248 1 1 Ethers ................................................................................... 250 12 Halides (see also: II.B.2.) ..................................................... 253 13 Nitriles and Imines ............................................................... 256 14 Other N-Containing Functional Groups .............................. 257 B Additions to Alkenes and Alkynes ............................................. 259 260 C Boron Compounds ...................................................................... D Nucleosides, Nucleotides etc ...................................................... 261 E Phosphorus, Selenium and Tellurium Compounds .................... 263 F Silicon Compounds .................................................................... 267 G Sulfur Compounds ...................................................................... 269 H Tin Compounds .......................................................................... 272 VII REVIEWS (see also: IV.M, VIII.A.5; VIII.C.7) A Techniques ................................................................................. 274 B Asymmetric Synthesis and Molecular Recognition .................... 276 C Reactions .................................................................................... 281 D Reactive Intermediates................................................................ 284 E Organometallics and Metalloids ................................................. 287 F Halogen Compounds and Halogenation (see also: VI.A.lO) ......293 G Natural Products ......................................................................... 294 H Others (see also: IV.M, VIII.A.5, VIII.C.6, VIII.F.7) .................299 VIII SELECTED TOPICAL AREAS A Fullerene Chemistry .................................................................... 306 ......................................... 306 Diels-Alder Type Cycloadditions 1 2 Other Cycloadditions ............................................................ 306 3 Photochemical Reactions ...................................................... 307 4 Other Fullerene Chemistry ................................................... 308 5 Reviews ................................................................................ 311 B Taxol and Related Taxane Chemistry ......................................... 312 C Dendrimers, Calixarenes and Other Unnatural Products ............315 1 Dendrimers ........................................................................... 315 a Dendrimer Synthesis ....................................................... 315 b Dendrimer Catalysts ....................................................... 318 c Hetero-Containing & Miscellaneous Dendrimers ..........318 2 Calixarenes ........................................................................... 319 a Calixarene Receptors ...................................................... 319

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b Synthesis of Calixirene ................................................... 320 c Synthesis on Calixirenes ................................................. 322 d Calixirene Isolation. Conformation. etc ......................... 323 3 Rotaxanes ............................................................................. 324 4 Supramolecules ..................................................................... 326 5 Cyclophanes .......................................................................... 328 6 Other ..................................................................................... 328 7 Reviews ................................................................................ 329 D Total Syn. of Selected Natural Products (see also: VII1.B).................329 E Reactions in Polar Media ............................................................ 346 1 Reactions in Aqueous Media ................................................ 346 2 Reactions in Ionic Media ...................................................... 351 F Combinatorial Chemistry ........................................................... 362 1 Supports. Linkers & Protecting Groups ................................ 362 2 Supported Reagents. Catalysts Ligands & Scavengers.........364 3 Solid-Phase Heterocyclic Synthesis...................................... 368 4 Solid -Supported Organic Reactions .................................... 372 5 Targeted Library Synthesis ................................................... 375 6 Novel Techniques in Combinatorial Chemistry ................... 377 379 7 Reviews ................................................................................ AUTHOR TNDEX ....................................................................................... 38 1


One of the more difficult problems facing chemists today is that of “keeping up with the literature.” For several reasons, the problem is particularly severe for the synthetic organic chemist. Bits of information of potential use are scattered throughout common chemistry journals and can be found in any paper, not just those dealing strictly with synthesis. Thus, synthetic chemists must read a large number of journals and must organize and index what they read to make the information available for future reference. Fewer chemists are doing this as electronic searching becomes more prevalent. The ability to leaf through a concise compendium of the recent literature still remains important. Thus, readers of such a collection can quickly see new developments in several areas of synthesis and, additionally, an abstract may catch their eye and catalyze a new research idea. The problem, however, is shared to some extent by all. Most organic chemists are at some time faced with the problem of synthesizing a desired material, and for many the problems are formidable. Nonspecialists faced with the synthetic problem are not likely to have kept pace with the developments in synthe tic chemistry that may well solve their problems, and they will not have the necessary information in their files, despite the capabilities of on-line searching Thus, we feel an organized annual review of synthetically useful information should prove beneficial to nearly all organic chemists, both specialists and nonspecialists in synthesis. It should help relieve some of the information storage burden of the specialist and should enable the nonspecialist who is seeking help with a specific problem to rapidly become aware of recent synthetic advances. Ideally also, it should appear as promptly as possible after the close of the abstracting period. As in the past years, we have placed particular emphasis on keeping the abstracts as concise as possible, while indicating the generality of the reactions involved. We have tried to combine similar publications into inclusive abstracts. This practice has allowed us to include a larger number of references without a substantial increase in the book’s length. It should be noted that where multiple references are included in the abstract, the first mentioned refers to the equation shown. The remaining references are related but not identical. To further aid the readers, we have separated related but less similar references from that represented by the graphic by the phrase “see also:”. We have allowed for two such separations per graphic. In a number of cases we xi

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PREFACE

have attempted to further elucidate the contents of these multiple references by including a statement below the graphic. If this statement is enclosed in square brackets [e.g. 1I.A. 1-2: “similar solvent free oxidation using CrO3” and 1V.D-1: “also with ally1 bromides”] then it pertains to data from the references following the lead reference. If round brackets are employed (e.g. I.E.3-4: “similarly for tetrhydrofurans and pyrrolidines” and 1I.A. 1-4; “also odorless Swern”) then further information about the lead reference is being provided. The year has been omitted from each reference as presumably all are from 2003. Any references from 2002 (journals received after our February 1 cutoff date) are noted appropriately. In an effort to be more space efficient, we have adopted letter abbreviations for the journal references from Katritzky’s Handbook of Heterocyclic Chemistry. See the List of Journals Abstracted for definitions of these letter abbreviations; they are alphabetized by the abbreviations rather than the journal name. Last year the Journal of the Chemical Society (Perkin I ) and (Perkin II) were combined into a new journal entitled Organic and Biomolecular Chemistv (OBC). In producing Annual Reports in Organic Chemistry2004 we have abstracted 43 primary chemistry journals, selecting useful synthetic advances. Only the common journals received by our libraries have been abstracted. We have also exercised selectivity in choosing which papers to abstract. Our general guidelines have been to include reactions and methods that are new, synthetically useful, or reasonably general. We have tried to present the information in an organized manner, emphasizing rapid visual retrieval. The purpose of this emphasis is to aid the reader in scanning the book. The mind is capable of absorbing a whole picture in an instant, but is considerably slowed by having to read sentences. If the pictures presented catch the reader’s interest, he or she should then seek details from the original paper. The author index is based on the name of the senior author(s) or sometimes the first author. No subject index is included because we feel the Table of Contents serves that fimction. Chapters 1-111 are organized by reaction type and, hopefully, the organization is self-explanatory; thus, there should be no difficulty in locating a new method of oxidation or a new cyclopropanation procedure. Chapter IV deals with methods of synthesizing heterocyclic systems. Where fused ring systems bearing multiple heterocyclic rings are shown, we have chosen to categorize the heterocyclic system by the ring formed in the reaction. Chapter V covers the use of protecting groups. Chapter VI deals with those synthetically useful transformations that do not fit easily into the first three chapters. In Chapter VII, the reviews have been divided into sections to help the reader to quickly find a review on a specific topic. Other area specific reviews may be found at the end of the section. Heterocyclic reviews may be found at the end of

PREFACE

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Chapter IV; Selected topical reviews are in VIII.C.7. Selected Topical Areas, consists of topical areas we felt are topics, and have collected titles of papers in these areas. While not an all inclusive listing, we hope it will prove useful. We organized the section on Total Syntheses of Selected Natural Products (V1II.D) so the synthesized target names (with associated author and reference) have been sorted and grouped alphabetically to help the reader locate a particular compound as quickly as possible. To keep the Annual to a reasonable size, only one author is listed in this section. We used our editorial prerogative to select from the many applicable syntheses. We maintain the section on Carbohydrates (VI.A.9) in the Useful Synthetic Preparations chapter, as well as the section divisions on Combinatorial Chemistry (V1II.F): 1 . Supports, Linkers & Protecting Groups; 2. Supported Reagents, Catalysts Ligands & Scavengers; 3. SolidPhase Heterocyclic Synthesis; 4. Solid-Supported Organic Reactions; 5 . Targeted Libraries Synthesis; 6. Novel Techniques in Combinatorial Chemistry; and 7. Reviews. Because of the increasing number of papers being published and the constraints placed on the number of pages we want AROS-2004 to be, we made further changes to the formating allowing more abstracts to be presented. We tightened the spaces between abstracts even further, and no longer use “and” when two or more authors are cited. Any undertaking of this type involves a series of compromises. We have chosen to emphasize reasonable cost and rapid visual retrieval of information at the admitted expense of detail and beauty. We would like to thank our readers over the past years for the wonderful reception they have given our endeavor. In passing on the editorship of AROS, two of us (KT, PMW) would like to acknowledge the excellent contributions made by our colleagues over the past 15 years as reflected in the high quality of AROS. It has been highly rewarding that scientists have communicated to us the usefulness of this series. We are proud of our speed to publication especially in the years before ChemDrawB. Comments (negative or preferably positive) or suggestions from the reader will be well received by the senior editor. Senior and Contributing Editor Philip M. Weintraub Contributing Editors Kenneth Turnbull Jeffrey S. Sabol Peter Norris


LIST OF JOURNALS ABSTRACTED Aldrichimica Acta Accounts of Chemical Research Acta Chemica Scandinavia Angewandte Chemie International Edition in English Australian Journal of Chemistry AJC Bulletin of the Chemical Society of Japan BCJ BMCL Bioorganic and Medicinal Chemistry Letters Journal of the Chemical Society Chemical Communications cc ccc Collection of Czechoslovakian Chemical Communications European Journal of Chemistry CEJ Chemistry and Industry (London) CKL) Canadian Journal of Chemistry CJC Chemistry Letters CL Chemical and Pharmaceutical Bulletin CPB Chemical Reviews CRV Chemical Society Reviews CSR EJOC European Journal of Medicinal Chemistry EJOC European Journal of Organic Chemistry Heterocycles H Helvetica Chimica Acta HCA JACS Journal of the American Chemical Society JCR(S) Journal of the Chemical Research (S) Journal of Heterocyclic Chemistry JHC Journal of Medicinal Chemistry JMC Journal of Organic Chemistry JOC Journal of Organometallic Chemistry JOM Monatschefte fur Chemie M Organic and Biomolecular Chemistry OBC Organic Letters OL OM Organometallics Organic Preparations and Procedures International OPP Organic Synthesis 0s Pure and Applied Chemistry PAC Russian Chemical Reviews RCR Synthesis S Synthetic Communications sc

AA ACR ACS

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LIST OF JOURNALS ABSTRACTED

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SL ST T TA TCC TL Z

Synlett Steroids Tetrahedron Tetrahedron Asymmetry Topics in Current Chemistry Tetrahedron Letters Zeitschrift fur Naturforschung, Teil B

GLOSSARY OF ABBREVIATIONS 4-PP pyrrolidinopyridine 9-BBN 9-borabicyclo[3.3. I]nonane 18-Cr-6 = 8-C-6 18-crown-6 AA amino acid Ac acetyl acac acetonylacetone ad adamantanyl ADC 9,lO-anthracene dicarbonitrile ADDP I , 1 '-(azadicarbony1)dipiperidine AIBN azobisisobutyronitrile ALB aluminum lithium bis(binaphth0xide) All ally1 Alloc = ALOC allyloxycarbonyl An p-anisyl APC ally1 palladium dimer APSG aminopropylated silica gel aq aqueous Ar aryl ATD aluminum tris(2,6-di-tertbutyl-4-meth ylphenoxide) ATPH aluminum tris(2,6diphenylphenoxide) AZMB 2-(azidomethyl)benzoyl BAlB bis-acetoxyiodobenzene BARF tetrakis[3,5-bis(trifluoromethy I)phenyl]borate BCN N-benzyloxycarbonyloxy-S-norbomene-2,3dicarboximide BDMS bromodimethyl-sulfonium bromide BDPP (2R, 4R) or (2S, 4s) 2,4bis(dipheny1phosphino)pentane

BER

borohydride exchange resin BICP (R,R) 2(R)-2'(R)-bis(diphenylphosphin0)1(R), I'(R)-dicyclopentane BIH bis(symcollidine)iodine(l) hexafluorophosphate BINAL-H LiAlHq/ethanol/l, 1'bis-2-naphthol complex BINAP = DINAP 2,2'-bis(diphenylphosphin0)-1,l binaphthyl BINAS 6-fold sulfonated 2,2'bis(diphenylphosphin0methyl)- l,I'-binaphthyl Bip biphenyl-4-sulphonyl BLA Bronsted acid assisted chiral Lewis Acid bmin 1-butlyl-3-methylimidazolium cation Bn benzyl BNAH l-benzyl-l,4-dihydronicotinamide BOB 4-benzyloxybutryl Boc t-butyloxycarbonyl BOM benzyloxymethyl BPO benzoyl peroxide bpy bipyridyl BQ benzoquinone BSA bovine serum albumin BSA N,O-bis-silylacetamide = 0,N-bis-trimethylsilyl acetamide Bt 1- or 2-benzotriazolyl BTAC benzyl triethylammonium chloride BTF benzotrifluoride Bth benzothiazole I-

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BTI BTI

PhI(02CCF3)2 [bis(trifluoroacetoxy) iodo]benzene BTEAC benzyl triethylammonium chloride BTFP 2-bromotri fluoroisoprene BTMA benzyl trimethyl ammonium BTS bis(trimethylsily1)sulfate BTSA bis-trimethylsilyl chromate BTSP bis(trimethylsily1) peroxide butyl Bu Bus tert-butylsul fonyl Bz benzoyl CAN ceric ammonium nitrate cat. catalyst benzyloxycarbony1 Cbz CCE constant current electrolysis CHD cyclohexadiene CHP cumene hydroperoxide Chx2BI dicyclohexyl iodoborane C1 FeTPP meso-tetraphenylphyrin iron chloride CMHP cumene hydroperoxide CMMP cyanomethylenetrimethylp hosphorane cod 1,5-~yclooctadiene cot cyclooctatriene Cp cyclopentadienyl CPTS collidinium-p-toluenesulfonate Cr-PILC chromium-pillared clay catalyst CRA complex reducing agent CSA camphor sulfonic acid CTAB cetyl trimethylammonium bromide CTACl cetyl trimethylammonium chloride

GLOSSARY OF ABBREVIATIONS

CTAN ceric tetra-N-butylammonium nitrate CTMS = TMCS chlorotrimethylsilyl Cu MeSAl copper(1) 3-methylsalicylate Cu TC copper(1) thiophene-2carboxylate Cy cyclohexyl A heat D day DABCO 1,4-diazabicyclo[2.2.2]octane DAMFA (diethylaminoethylene) hexafluoroacetylacetone DAST diethylaminosulfurtrifluoride DATMP diethylaluminum 2,2,6,6-tetramethylpiperidide dba dibenzylidene acetone DBAD=DTBAD di-tertbutylazodi-carboxylate DBH di-tert-butyl hyponitrite DBI dibromoisocyanuric acid DBn p-dodecyloxybenzyl dbpp 1,3-bis(dibenzophospholy1)propane DBPO Di-tertbutyl peroxyoxalate DBS dibenzosuberyl DBSA dodecylbenzylsulfonic acid DBTA dibenzyl L-tartramide DBU I ,5-diazabicyclo[5.4.0]undec-5-ene DCA 9,lO-dicyanoanthracene DCB dichlorobenzene DCC dicyclohexylcarbodiimide DCE 1,2-dichIoroethane DCN 1,4-dicyanonaphthalene Dcpm dicyclopropylmethyl


2,3-dichloro-5,6-dicyanobenzoquinone de = d.e. diastereomeric excess DEAD diethyl azodicarboxylate DEPC diethyl cyanophosphor idate DEPO diethylphosphine oxide DET diethyl tartrate DHAP dihydroxyacetone phosphate DHP dihydropyran DHQD dihydroquinidine DIAD diisopropylazodicarboxylate DIB (diacetoxyiod0)benzene DIBAH = DIBAL diisobutylaluminum hydride DIM 2-(hydroxyethy1)- 1,3dithiane DIMCARB dimethylammonium dimet hy 1 carbamate DIOP 2,3-O-isopropylidene-2,3dihydroxy-l,4-bis(diphenylphosphin0)butane dippp 1,3-bis(diisopropylphosphino)propane DIPT diisopropyl tartrate DLP dilauroyl peroxide DMA N,N-dimethylacetamide DMAD dimethyl acetylene dicarboxylate DMAP 4-(N,N-dimethyl)aminopyridine DMB rn-dimethoxybenzene Dmb 2,4-dimethoxybenzyl DMB 2,3-dimethylbuta-l,3diene DMBQ 2,6-dimethyl-l,4benzoquinone DMD dimethyl dioxirane DME dimethoxyethane DDQ

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DMF dimethylformamide DMFDMA dimethylformamide dimethyl acetal DMG directed metalation group DMI 1,3-dimethylirnidazolidin2-one DMM dimethoxymethane DMN 1,5-dimethoxynaphthalene DMP Dess Martin Reagent DMP 2,6-dimethylphenol DMPS dimethylphenylsilyl DMPU N,N'-dimethylpropyleneurea DMSO dimethylsulfoxide DMT 4,4'-dimethoxytrityl DMTMM 4-(4,6-dimethoxy[ 1,3,5] triazin-2-yl)-4-methylmorpholinium chloride DMTr dimethyltrityl DNBA 2,4-dinitrobenzoic acid dpba 2-(dipheny1phosphino)benzoic acid dpma N,N,-di(pyrroly1-amethyl)-N-methylamine DPC diphenylphosphoro chloridate DPDC diisopropyl peroxydicarbonate DPDM diphenyl diazomethane DPEDA 1,2-diphenylethane- 1,2diamine DPM diphenylmethyl DPPA diphenylphosphorazidate dppb bis( 1,4-diphenylphosphino)butane dppe = DPPE bis(dipheny1phosphino)ethane dppf dichloro[ 1,l'-bis(diphenylphosphinoferrocene)]

xx

1,3-(dipheny1phosphino)propane DPS t-butyldiphenylsilyl DPTC O,O'-di(2-pyridyl) thiocarbonate dr diastereomeric ratio ds diastereoselectivity DTBAD = DBAD di-tertbutylazodi-carboxylate DTBB 4,4'-di-tert-butylbiphenyl DTBP 2,6-di-t-butylpyidine dfBPF 1,1'-bis(di-tertbuty1phosphino)ferrocene DTE dithioerythritol DTPM [ 1,3-dimethyl-2,4,6-(1 H, 3H,SH)-trioxopyrimidin5-ylidinelmethyl E general electrophile EDAC ethyldimethylaminopropylcarbodiimide EDC l-ethyl-3-(3-dimethylaminopropy1)carbodiimid e EDCP ethylene dicarboxylic diphosphonic acid EDTA ethylenediamine tetraacetic acid ee = e.e. enantiomeric excess en ethylene diamine EPHP N-ethylpiperidine hydrophosphorous acid Et ethyl EWG electron withdrawing W U P Fc ferrocenyl FDMA formaldehyde dimethyl acetal FDP fructose-l,6-diphosphate Fe(dbm)3 tris(dibenzoy1methido) iron(1I I) dppp


FePHEN tris( 1,lO-phenanthroline)iron(III)hexafluorophosphate Fe(Epp) iron(II1) tetraphenylporphyrin fl flavin FI 9-fluorenyl flosyl = Fs fluorosulfonate Fmoc 9-fluorenylmethoxycarbonyl fod 6,6,7,7,8,8,8-heptafluoro2,2-dimethyl-3,5-octanedione FSM mesoporous silica Fs = flosyl fluorosulfonate FTT 1-fluoro-2,4,6-trimethylpyridinium triflate FVP flash vapor pyrolysis GaSO chiral Ga heterometallic complex GEBC gel entrapped base catalyst Gr graphite GSNO nitrosoglutathione Gltco-PTS glycosyl phenylthiosulfonate h hours Hap hydroxyapatite HDNIB [hydroxy(2,4-dinitrobenzenesulfonyloxy)iodo] benzene hfacac hexafluoroacetylacetone HFIP hexafluoro-2-propanol HGK 4-hydroxy-2-ketoglutarate HLADH horse liver alcohol dehydrogenase HLE horse liver esterase Hmb 2-hydroxy-4-methoxybenzyl HMDS 1,1,1,3,3,3hexamethyldisilazane


HMPA = HMPT hexamethylphosphoramide HMS hexagonal mesoporous silica HMTAB hexamethylenetetramine bromide HNIB [hydroxyb-nitrobenzenesul fonyloxy)iodo] benzene hv irradiation with light HPA heteropoly acid 3-HQD 3-hydroxyquinuclidine HTIB [hydroxy(p-tolylsulfony loxy)iodo]benzene IBDA iodobenzene diacetate IBX o-iodoxybenzoic acid IDCP iodonium dicollidine perchlorate I MesH2 1,3-dirnesyl-4,5dihydroimidazole-2ylidene INOC Intramolecular Nitrile Oxide Cycloaddition Ipc2 diisopropylcamphyl IPr 1,3-bis(2,6-diisopropylphenyl)imidazol-2ylidene K- 10 a Montmorillonite clay KMBA potassium Nmethylbutyramide KSF a Montmorillonite clay LA Lewisacid L-selectride" lithium triSbutylborohydride L.R. Lawesson's reagent LAH lithium aluminum hydride LBDE lithium perchlorate in Et20 LDA lithium diisopropylamide LDBB lithium 4,4'-tbutylbiphenylide LDE lithium diethylamide

xxi

LDPE lithium perchloratediethyl ether LICKOR BuLiltBuOK liq. liquid LR Lawesson's reagent LTMP lithium 2,2,6,6-tetramethylpiperidide MABR methylaluminum bis(4brom0-2,6-di-~butylphenoxide) MAD methylaluminum bis-(2,6di-tbutyl-4-methylphenoxide) MAPh methylaluminumbis(2,6diphenoxide) MBDA magnesium bis(diisopropylamide) MBT 2-mercaptobenzothiazole MCPBA m-chloroperbenzoic acid MCM-4 1-TBD hybrid organic/ inorganic reusable catalyst Me methyl Mek methyl ethyl ketone MEM p-methoxyethoxymethyl MEPY methyl 2-pyrrolidone5 (S)-carboxylate Mes = mesityl 2,4,6-trimethylphenyl MMPP magnesium monoperoxyphthalate Mmt 4-methoxytrityl Mn(phox)3 tris(2-oxazoliny1)phenato manganese@) MOM methoxymethyl MPD 1-methylpyrrolidone MPM methoxy(phenylthi0)methyl Mpm = PMB p-methoxybenzyl MPPC N-methyl piperidine chlorochromate MS molecular sieves

xxii

methanesulfonyl methanesulfonic acid o-mesitylenesul fonyl hydroxylamine Mspoc 2-methylsulfonyl-3phenyl- 1-prop-2-enyloxycarbonyl MTO methyltrioxorhenium (MeRe03) MTPA methoxy-a-trifluoromethylphenylacetyl MV2+ methyl viologen MVK methyl vinyl ketone mw = pW microwave NaBMGS sodium butylmonoglycosulfate NAP naphthylmethyl Naph = Np naphthyl NBS N-bromosuccinimide NCS N-chlorosuccinimide NCP N-chloro-3-methyl-2,6diphenylpiperidin-4-one NDMS 2-norbornyldimethyl silyl neocuproine 2,9-dimethyl-l,10phenanthroline Nf nonaflate Nf nonafluorobutylsulfonyl NfF nonafluorobutane sulfonyl fluoride NFOBS N-fluoro-O-benzenedisulfonimide NHPI N-hydroxyphthalimide NIS N-iodosuccinimide NISac N-iodosaccharin NMM N-methyl morpholine NMO N-methylmorpholine-Noxide Nph neophyl NPM N-phenylmaleimide N-PSP N-phenylselenophthalimide NR no reaction Ms MSA MSH


Ns Nuc. [O] ODCB ONf

2-nitrobenzenesulfonyl general nucleophile general oxidation o-dichlorobenzene nonaflate= nonafluoro- 1butanesul fonyl Oxone potassium peroxymonosulfate PBP pyridinium bromide perbromide PCC pyridinium chlorochromate PDC pyridinium dichromate PEG polyethylene glycol Pf 9-phenylfluorenyl pfb perfluorobutyrate PFC pyridinium fluorochromate Ph phenyl Ph-H benzene Ph-Me toluene PHOX 2-[2-(dimethyl(phosphin0)-phenyll-4phenyl-4,Sdihydrooxazole Pht tetra-tert-butylphthalocyanine PhTRAP 2,2'-bis[ 1-(diphenylphosphino)ethyl]- 1,1'biferrocene pic 2-pyridinecarboxylate PIDA phenyliodonium diacetate PIFA phenyliodo bis(trifluoroacetate) PLAP porcine liver acetone powder PLEPIG LIVER ESTERASE PMHS polymethylhydrosiloxane PMB = Mpm p-methoxybenzyl PMP 1,2,2,6,6-pentamethylpiperidine PMP p-methoxyphenyl

xxiii


PNB p-nitrobenzyl PNP dimer cis, exo-2-phenylnorbornylpalladium CIp-nitrobenzyloxycarbon yl PNZ polyphosphoric acid PPA ethyl polyphosphate PPE PPHF pyridinium polyhydrogen fluoride 2-pheny1-2-(2-pyridyl) PPI imidazole pig pancreatic lipase PPL pol y(p-phenylene) PPP PPSE polyphosphoric acid trimethylsilyl ester PPTS pyridinium p-toluenesul fonate Pr P'OPYl propargy loxycarbony 1 Proc PSCBH poly supported cyanoborohydride PSDIB poly[4-(diacetoxy) iodostyrene] PSE phenylsulfonylethylidene psi pounds per square inch PTAB phenyltrimethylammonium perbromide PTC phase transfer catalysis PTMSE (2-phenyl-2-trimethylsily1)ethyl PTOC pyridine-2-thione-Noxycarbony 1 PTS p-tolylsulphonate PTSA p-toluenesulfonic acid PTT phenyltrimethylammonium tribromide pyr pyridine QFC quinolinium fluorochromate QxDC quinoxalinium dichromate rac racemic RaNi Raney nickel

Rf ROMP rt Salen

perfluorinated alkyl ring-opening metathesis room temperature N,"-ethylenebis(salicyl ideneim inato) SAMP (s)-1-amino-2methoxymethylpyrrolidine SBER sulfurated borohydride exchange resin SC C 0 2 super critical C02 SDS sodium dodecylsulfate SEM = TEOC p-trimethylsilylethoxymethy 1 SES 2-[(trimethylsilyl)ethyl]sulfonyl Sia Siamyl Si-BEZA 0-(trisubstituted sily1)benzamide Si-PTA silica-supported phosphotungstic acid SMEAH sodium bis(2-methoxyethoxy)aluminum hydride SPB sodium perborate SPC sodium percarbonate T3p@ propane phosphonic acid anhydride TABCO 2,4,4,6-tetrabromo-2,5cyclohexadienone TADDOL 2,2,-dimethyl-a,a,a1, a*-tetraaryl-I ,3-dioxolan4,5-dimethanol TASF tris(dimethy1amino)sulfur(trimethylsily1)difluoride TBAB tetrabutylammonium bromide TBAF tetrabutylammonium fluoride TBAHS tetra-n-butylammonium hydrogen sulfate

xxiv

TBAT tetrabutylammonium trifluorodi fluorosilicate TBATB tetrabutlyammonium tribromide TBATFA tetrabutylammonium tri fluoroacetate TBATFA tetrabutylammonium tri fluoroacetate TBCO tetrabromocyclohexadienone TBDMS = TBS t-butyldimethylsilyl TBDPS butyldiphenylsilyl TEAB tetraethyl ammonium bromide Tbfmoc Tetrabenzo[a,c,g,i] fluorenyl- 17-methyloxycarbonyl TBH di-tert-butyl hypochlorite TBHP tbutyl hydroperoxide TBME tbutyl methyl ether TBP tributylphosphine TBST triphenyl silanethiol Tbs 4-methoxy-3-t-butylbenzenesulphony1 TBSOP N-fbutylcarbonyl-2(tbutyldimethylsi1oxy)pyrrole TBTH tributyltin hydride TBTSP t-butyl trimethylsilyl peroxide TCAA trichloroacetyl anhydride TCCA trichloroisocyanuric acid TCEP tris(2-carboxyethy1)phosphine TCF trichloromethyl chloroformate TClCA trichlorocyanuric acid TCNE tetracyanoethylene TCNEO tetracyanoethylene oxide


TDTAP tetradecyl trimethylammonium permanganate TCPCTFE (tetrakis(2,2,2-trifluoroethoxycarbony1)palladium cyclopentadiene TDS dimethyl thexylsilyl TEA triethylamine TEAA tetraethylammonium acetate TEAF triethyl ammonium formate TEAP tetraethyl ammonium perchlorate TEBA Benzyl trimethylammonium chloride TEEDA N,N,N',N'-tetraethylethylenediamine TEOC = SEM p-trimethylsilylethoxymethyl TEP triethylphosphite TES triethylsilyl Tf trifluoromethanesulfonyl TFA trifluoroacetic acid TFAA trifluoroacetic anhydride TFE trifluoroethanol TFFH tetramethyl fluoroformamidinium hexafluorophosphate TFMSA trifluoromethanesulfonic acid TFO methyl(trifluor0methy1)dioxirane TFP 1,1,1-trifluoro-2-propanol TFP tris (2-fury1)phosphine TFPZ trifluoroisopropenyl zinc TFSA trifluoromethanesulfonic acid THAB tetrahexylammonium bromide THAH tetrahexylammonium hydrogen fluoride thexyl 2,3-dimethylbutly

xxv


THF tetrahydrofuran THFA tetrahydrofurfuryl alcohol THP tetrahydropyranyl TIBA tri(isobuty1)aluminum TIBAL tri-iso-buylaluminum TIPPSe-Br (2,4,6-triisopropylpheny1)selenium bromide TIPS tri-ipropylsilyl TMABr tetramethylammonium bromide TMACC trimethylammonium chlorochromate TMAF tetramethylammonium fluoride TMAO = TMANO trimethylamine N-oxide TMATB trimethylammonium tribromide TMEDA tetramethylethylenediamine TMG 1,1,3,3-tetramethyIguanidine TMHI 1, 1, l-trimethylhydrazinium iodide Tmob 2,4,6-trimethoxybenzyl TMP 2,2,6,6-tetramethylpiperidine TMS trimethylsilyl TMSA trimethylsilyl azide = azido trimethylsilane TMSDEA N,N-diethyltrimethylsilylamine TMU tetramethylurea TNM tetranitromethane t-OcNC 1,1,3,3-tetrarnethylbutyl isocyanide To1 tolyl Tos = Ts p-toluenesulfonyl

Tp trispyazole borate TPCD tetrapyridine cobalt(I1) dichromate TPP Tetraphenylporphyrin TPP triphenyl phosphine TPP triphenylphosphate TPPB tris(pentfluor0pheny1)borane tppts m-sulfonated triphenylphosphine = tris(psulfonatopheny1)phosphine tpy terpyridine Tr = trityl triphenylmethyl Tsc 4-trifluoromethylphenylsu1fonyl)ethoxycarbonyl Ts-MIC tosylmethyl isocyanide TSE 2-(trimethylsilyl)ethyl TTBP 2,4,6-tri-tertbutylpyridine TT Co(I1) Pc tetrabutylammonium cobalt(I1) phthalocyanine5,12,19,26-tetrasulfate TTMPP tris(2,4,6-trimethoxypheny1)phosphine TTMSS tris(trimethylsily1)silane UHP urea-hydrogen peroxide complex wk week Z benzyloxycarbonyI Zr BDC Zr (BH&C12(DABCO)*

@ - = Q polymeric support @*= US ultrasound *

Denotes asymmetric center


I CARBON-CARBON BOND FORMING REACTIONS

I.A. Carbon - Carbon Single Bonds (see also: I.E., I.F., I.G., I.H.) I.A.1. Alkylations of Aldehydes, Ketones and Their Derivatives I.A.I-1 Liu, X.; Hartwig, J.F., OL, 5, 1915; Zhang, H. et al., SL, 2228. R

.~% Ph

Pd(dba)2, (Ad)2PtBu O + Ar-Br

K2CO3,Ph-Me

Ar O

~ Ph

40-85% I.A.1-2 Cho, C.S.; Shim, S.C. et al., OM, 22, 3608. OH OH OH R~"~Me + LR1 RuCI2(PPh3)3'KOH .1~ R ~ , , . ~ R 1 1-dodecene, dioxane, 80~ 25-90% I.A.1-3 Posner, G.H. et al. JOC, 68, 3049.

o

~o,. ~,,,,,,~ 1. LDA, THF, -280C

+

2. BF3oEt2O, THF, -78~ 3. H2, Pd/C, EtOH 62-70% I.A.1-4 Tanyeli, C.; Ozdemirhan, D., TL, 44, 7311. O O R ~ n

Mn(OAc)3'Bn'Br Ph-H, 80~

R ~ P h n

38-65%

2

ORGANIC SYNTHESIS--2004

I.A.1-5 Hidai, M.; Uemura, S. et al., OM, 22, 873; Campos, K.R.; Journet, M.; Cai, D. et al., JOC, 68, 2338. R ~ [Cp*RuCI(rr~-SR*)]2 P~ + Y NH4BF4,60~C OH O O 41-95%

ee = 10-35% I.A.1-6 Nakamura, M.; Nakamura, E. et al., JACS, 125, 6362. R1

R3,tnR

0

Me

CH2=CH2 H3 O+

94-99% ee = 58-98 %

I.A.1.7 Evans, P.A.; Leahy, D.K., JACS, 125, 8974. R

O

~OCO2Me

+ LiaR1

R

P(OMe)3,THF, 0oC_~rt

O

~~~JLR1 66-85%

I.A.1-8 Ma, J.-A.; Cahard, D.; JOC, 68, 8726; Grainger, R.S. et al., JOC, 68, 7889. "Mild Eleetrophilie Trifluoromethylation of -Ketoesters and Silyl Enol Ethers with 5-Trifluoromethyl-dibenzo-thiophenium Tetrafluoroborate."

I.A.2. Alkylations of Nitriles, Acids and Acid Derivatives

I.A.2-1 Bauta, W.E. et al., JOC, 68, 5967. CO2Et ~

CO2Et TMG, TEA M e ( ~ ~ M e --~O CIOC~J~Me MeCN, 0oC Meu

U

86%

CARBON-CARBON BOND FORMING REACTIONS

3

I.A.2-2 Takeda, K. et al., JOC, 68, 9330. OTBDMS R-X, NaHMDS.-~ TBD CN THF, .800C TBD

OTBDMS ~ N

C

80-99%

I.A.2-3 You, J.; Verkade, J.G., AG(E), 42, 5051. 9

D

iBui"

.BU.N.~-~.'~6/~"Bu

S1

Cl

R1

~"~N~

CN +

112 Pd(OAc)2or Pd2(dba)3 base, Ph-Me, 90~

10-96%

I.A.2-4 Maruoka, K. et al., AG(E), 42, 579 and TA, 14, 1599; Castle, S.L.; Srikanth, G.S.C., OL 5, 3611; Kumar, S.; Ramachandran, U., TA, 14, 2539. Ph2C .L-AA-OtBu R-X, chiral PTC Ph2C L-AA-OtBu ~"~O

50% aq KOH, Ph.Me, 0*C"~

~"'~O R 80-95% de = 90-98 %

I.A.2-5 Hruby, V.J. et al., TL, 44, 5863; Soloshonok, V.A. et al., TL, 44, 1063; Kawabata, T. et al. T, 59, 965. Ph Ph

~O I

Ph

. . . .

Br"J~"~

~ L ~ ~

H

N a O H , D M F , -30oc

96% i ~ H : a - H = 12:1

I.A.2-6 Wanner, T. et al. EJOC, 2233. MeO MeO

k___

BU

o -~,--,

~__~

,O T i S

80.C, 2hPtBu4 Me ~ ~" DME/THFl~tBi~X o

"

OTBS M e O

X---r~

, e - - ~" +tMe BtiX o

72% 9:7:3:1

O OTBS

4

ORGANIC SYNTHESISm2004

I.A.2-7 Chen, Y.; Yudin, A.K., TL, 44, 4865; Takemoto, Y. et al. AG(E), 42, 2054. Ph2C ].OAc Pd(OAc)2,BINAP Ph2~'~CO2 R ~.~CO2 R -I- Ph2C~--,.CO2R Nail, MeCN, rt Ph2C~N,~,,.CO2R

84% d,hmeso = 2:1 I.A.2-8 Trost, B.M. et al., JACS, 125, 4438.

g

/OBh

eh'~oNo~o "1" ~,~ OBn

Pd(O2CCF3)2'CH2CI2~ ph.~NoN~'oH ~NH~~~

67-87% dr = 13-20:1 ee =85-94%

~.....~PPl~ P h 2 P ~

I.A.2-9 Ley, S.V. et al., CC, 468; Munoz-Munoz, O.; Juaristi, E., T, 68, 4223; Shih, N.-Y. et al., OL, 5, 4249. MeO MeO R X

OMe

O LDA,HMPA/THF, -78~-550C

I.A.2-10 Cossy, J. et al., SL, 2171. 1. SBuLi,ZnCI2, -200C ~ 0 2. Ar-Br, NMez Pd(dba)2 ~

Bn cy2e

J,-

R OMe "-" 72-92% dr = 2-22:1

~,~~r

Bn 70-98%

I.A.2-11 Thebtaranonth, Y. et al., JMC, 46, 2397; Paintner, F.F. et al., SL, 627. C ~ EtO2C./----~ g-x EtO2 Ph Nail, DMF/THF, rt 65-76%


5

I.A.2-12 Kawabata, T. et al., CC, 162. DMe Me-I P hN/ Y RRI~ O

MeO .Me 1 ph~ NRR

LTMP,TBME,-78*C

0 17-72% ee = 0-64%

I.A.2-13 Jubault, P.; Pannecoucke, X. et al., TA, 14, 1637. E OH OH E-X Ph2__~~~ '] BuLi, additive, -78-~-20~ ~H 3 0 Ph BH3 0 Ph

P er LrJ

v

32-90% de = 15-98% I.A.2-14 Chang, N.-C. et al., JOC, 68, 5688. R1

R1 s

R-X Nail, THF Re

81-88%

I.A.3. Alkylations of 13-Dicarbonyl, 13-Cyanocarbonyl Sy.stems and Other Active Methylene Compounds I.A.3-1 Kuwano, R. et al., JACS, 125, 12104; Kuwano, R.; Uchida, K.; Ito, Y., OL, 5, 2177. 2Et BSA, KOAc, DPPF Ar~OCO2Me + R CO2Et pd(rl3.C3H5)(cod)BF4

Av

'C.~RO2Et CO2Et 61-99%

I.A.3-2 Nakamura, M.; Endo, K.; Nakamura, E., JACS, 125, 13002. O O R1

R2 neat,100-1400C 76-99%

6


I.A.3-3 Carretero, J.C. et al., JOC, 68, 3679; Brunner, H. et al., TA, 14, 1115; Bolm, C. et al., OBC, 1, 145; Ohta, T. et al., TA, 14, 537; Hou, X.L. et al., TA, 14, 107; Mino, T. et al., JOM, 665, 122; Douthwaite, R.E. et al., OM, 22, 4187; Kim, T.-J. et al., OM, 22, 1475; Moberg, C. et al., OL, 5, 2275; Tamaru, Y. et al., T, 59, 7767; Knochel, P. et al., TA, 14, 255; Wallner, O.A.; Szabo, K.J., JOC, 68, 2934; Moberg, C. et al., JOC, 68, 3258; Kurita, J. et al., TL, 44, 6217; Nakano, H. et al., TA, 14, 2361. Nut-H, [Pd(h3-C3Hs)CI]2 OAc ~uc THF or CH2CI~ rt Ph Ph Ph'/~""~Ph ~ . , ~ ~ 50-97% Fe PR,2 SR ee = 40-99 % I.A.3-40kano, T. et al., JOM, 676, 43. OCO2Et Pd cat., PPh3, tBuONa ph,,~l~ ph 4- CH2(CO2Et)2 ~

CH(CO2Et)2 ph~,~,,~ph 31-77%

I.A.3-5 Malacria, M. et al., JOC, 68, 5588. ___(SIR3 Pal(OAt)2, PPh3 ,SIR3 + CH2(CO2Me)2 ~AcO__~ / CO2Me AcO----/ ~-- OAc THF, rt ~\~O2Me 64-99% e:z= 1-100:1 I.A.3-6 Mori, M. et al., OL, 5, 31. CI"

O 4- CH2(CO2Me)2

_CH(CO2Me)2

1. CsCO3, RI~NR Pd2(dba)3"CHCl3 ~ 2. CH2N2,Et20

r

CO2Me 63%

I.A.3-7 Yang, D. et al. OL, 5, 2869; Krafft, M.E.; Lucas, M.C., CC, 1232; Fukuyama, Y. et al., TL, 44, 6235. O O O O O O Ln(OTf)3, dioxane

~'~-='~R 1 H

or

I

31-97%

_~,,,R 1 iI


7

I.A.3-8 Maruoka, K. et al., AG(E), 42, 3796; Covarrubias-Zuniga, A. et al., SC, 33, 3165. O R-X, CsOH'H20, Ph-Me,-40~ ~~CRO2tBu

o2t u

Ar Br"

90-99%

e.e. = 87-96%

I.A.3-9 Trost, B.M.; Jiang, C., OL, 5, 1563. O EtO2C~~,,

SPh j 4- ~ ~ ' ~ O

OH Pdz(dba)3.CHCl3, lig EtO2C-~~ N , , / S P h CH2C12,rt 71% ee = 94 %

I.A.3-10 Hadjiarapoglou, L.P. et al., T, 59, 7929. O r + Phi +'~" SO2Ph MeCN,rt

O

SO2Ph

~(Y'~r 42-66%

I.A.4. Alkylations of N-, P-, S-, Se and Similar Stabilized Carbanions

I.A.4-1 Katritzky, A.R. et al., JOC, 68, 1443" Koo, S. et al., HCA, 86, 2620.

R1 R2 RSOf,,,J + B t ~ O

R1 BuLi 2~R2 TItF, .78C~ RSO O 73-96%

I.A.4-2 Uneyama, K. et al., TL, 44, 6319; Shipman, M. et al., CC, 1344; Mural, T. et al., JOC, 68, 8514. Tsh~ E+' BuLi TsIN~'E w" CF3 THF, .102oc ~" "CF3 13-95%

8


I.A.4-3 Smith, III, A.B. et al., JACS, 125, 14435. R1 R ~ ~ O 1" tBuLi, Et20, "78-"25~ ~S

+

TBSO ~ S

2. E + HMPA, -78--,00C

TBS 56-74% I.A.4-4 Afarinkia, K. et al., S, 357.

+ R-X

LDA TI

,

.~'-

(EtO)2P~O

(EtO) O

34-81% I.A.4-5 Afarinkia, K. Jones, C.L., S, 509; Afarinkia, K. et al., SL, 513; Lequeux, T. et al., OBC, 1, 2486. E +, LDA ,..._ ~ . _ . Ph BnN,,.LT-O | Ph-Me,-78~ 6~~Me e E 40-64% d.r. = 1-15:1 I.A.4-6 Hodgson, D.M. et al., OBC, 1, 4293. ~~

O + EtCONMe2

_O•__Et

BuLi, sparteine Et20, -900C

57%

ee = 74% I.A.4-7 Falck, J.R. et al., OL, 5, 4759; Rychnovsky, S.D.; Takaoka, L.R., AG(E), 42, 818. PC~_x PC.,,x

SnBu3 R/~OyNR12 S

E+, CuI THF, 50~ "~ R ~

E OyNR12 S

45-96%


9

I.A.4-8 Naud, S.; Cintrat, J.-C., S, 1391; Fleming, I.; Russell, M.G., CC, 198.

+

Bu3Sn,~ ~ "~ Bn

R ~ I O BuLi ~- ~ R O ~ ~ 1 , -100~

n

26-57%

I.A.5. Alkylations of OrganometaUic and Related Reagents (see also: I.B.3., I.B.4., I.F., I.G.) I.A.5-1 Zhou, J.; Fu, G.C.; JACS, 125, 12527. RCH2-X + R1.ZnX, Pd2(dba)2,PCyp3,NMI NMP/THF, 80~ I.A.5-2 Kambe, N. et al., JACS, 125, 5646. NiC!2 or CuCl2 R-F + R1-MgX

R~R 1 52-90%

R.R1 38-98%

I.A.5-3 Murphy, K.E.; Hoveyda, A.H., JACS, 125, 4690. iprO2C~ Et2Zn,(CuOTf)2.PhH,TI-IF i p r O 2 C ~ (EtO)211P-'O

~

r

0

~on

n o

H Et

o eu

ee=94%

I.A.5-4 Marek, I. et al., OL, 5, 5087. R --

~ Nipr2

R•R1

R-Cu, MgBr2,Et20 then E-X

~~'-Sier2

40-78%

I.A.5-5 Arrayas, R.G.; Cabrera, S.; Carretero, J.C., OL, 5, 1333; Nakamura, M.; Nakamura, E. et al., OL, 5, 1373. OH R-MgX, CuCI,PPh3

~

-OR

Ph-Me, rt 47-94% anti:syn = 9-49:1

10


I.A.5-6 Shinokubo, H.; Oshima, K. et al., OL, 5, 4623. R

\

/

R1

E

CH2=CHCH2MgCi,MnCI2,THF

\R 2

R~ . ~

~

~

then E+ 0~ 34-78%

I.A.5-7 Brion, J.-D.; Ardisson, J. et al., S, 2530 and SL, 955. R

~-~

Li

1" E R2CuCNLi2 E-X 2 . H~~-~--~ 57-95%

I.A.5-8 Martynov, A.V. et al., JOM, 674, 101. NiClz(dppe) or NiCl2(dppp) EtSe~-~SeEt + R-MgBr

R

R

78-85% I.A.5-9 Tenenbaum, J.M.; Woerpel, K.A., OL, 5, 4325. BnO

BnOPh2Sj--0 ipr

1. CH2=CHCH2TMS,SnCI4, Ph-Me 2. H202, KF, KHCO3,MeOH/THF

~- ipr

OH

OH

I~,~ ~,~ ~ , ~ Me

Me

56%

I.A.5-10 Yoshida, H.; Kunai, A. et al., CC, 1510. Pal(OAt)2, dppp R.SiMen(OR1)m DMSO or DMSO/H20/O2

R-R 11-94%

I.A.5-11 Hodgson, D.M. et al., OBC, 1, 1139; Zhao, H.; Pagenkopf, B.L., CC, 2592; Smith, III, A.B. et al., OL, 5, 2751. ( ~

BuLi,Ph'Me, "780C~_ o ~ B U ip~

ipr

' N

H

N

~~

~O

OH

49% ee=49%

Et Et

I.A.5-12 Luzzio, F.A.; Mayorov, A.V., SL, 532. Phth~,,],_,~Cl

Pd(0),Nuc/NuC-HTHF, 0oc _~ P h t h N ~ . , ~ u c 34-99%

iq


11

I.A.5-13 Gansauer, A. et al., CEJ, 9, 531; Lu, Y.; Li, C.-J. et al., CC, 2318. OH Rr + ~'~ "CO2tBu Cp*2TiCI,Zn ~..- R ~ c o 2 t B u 2,4,6-coludine.HCl R

R 68-90%

dr = 1.1-9:1 I.A.5-14 Smith, K. et al., S, 2345; Wu, G.G. et al., JOC, 68, 4984. H

~

~

H

E+BuLi ~~ R THF,-78*C

~

R 70-80% E

I.A.5-15 Kraus, G.A.; Choudhury, P.K., S, 659; Harmata, M.; Kirchhoefer, P., SL, 497; Harmata, M.; Wacharasindhu, S. CC, 2492. Br E Br _ _ ~ ~ ~

Me

E+' B u L i ~

THF, -78~

Br _ ~ ~

one/..._ Me 85-98%

I.A.5-16 Yus, M. et al., TL, 44, 5025 and T, 59, 8525. E+, Li, DTBB CaH17.F .~.- C8H17-E 53-98% I.A.5-17 Theberge, C.R.; Zercher, C.K., T, 59, 1521. O O PGH~~CO2Me CH212'EI2Zn ~ P G H ~ c o 2 M -

R

R

25-68%

I.A.5-18 Khwana, J.M. et al., OBC, 1, 1737. R

iron(II) oxalate

R

Ar

Ar~'---X HMPA/DMF,155-160~ 37-85%

e

12


I.A.6. Other Alkylation Procedures I.A.6-1 Flynn, B.L. et al., CC, 1380. O R

/

frO XR1

1. Bu3SnH, Pd(PPh3)4 2. R-X, CuCI

R

48-93%

I.A.6-2 Kern, O.T.; Motherwell, W.B., CC, 2988. tBu--N~ + p h , ~ O +

R-CO2H

O O LiOTf .~ N~,,,.~O ~ THF, reflux tBuH R Ph 64-77%

I.A.7. Nucleophilic Addition to Electrophilic Carbon

l.A.7.a.1. Aldol-Type 1,2-Additions l.A.7.a.l-1 Evans, D.A. et al., JACS, 125, 8706; Crimmins, M.T.; Mc Dougall, P.J., OL, 5, 591; Romea, P.; Urpi, F. et al., SL, 1109; Hitchcock, S.R. et al., TA, 14, 3233; Casper, D.M.; Hitchcock, S.R., TA, 14, 517; Spanu, P. et al., TL, 44, 671; Hein, J.E.; Hultin, P.G., SL, 635. S O TMS-OTf, 2,6-Me2Pyr S O OH ~ ~ M CH2CI2/Ph'Me' "78-~'20~ ~ s ~ N ~ + R-CHO TrO OTf R e ~~o~~~ ~ Me 46-86% syn:anti = 6-49:1 syn ee = 91-97 % I.A.7.a.l-2 Yadav, V.K.; Balamurugan, R., OL, 5, 4281. TMS OH O R ~ + O TiCi4 R~H R Me R1AR2 CH2C12,-780C 45-79% a-H:I~-H= 2-12:1


13

I.A.7.a.l-3 Shibasaki, M. et al., JACS, 125, 2169; Enders, D.; Burkamp, F., CCC, 68, 975; Adam, W.; Zhang, A., EJOC, 587. O OMe OH O OMe

o /'6 t2ZnliedlNO,

81-95% syn:anti = 2.57-32.3:1 syn ee = 87-99 %

I.A.7.a.1-4 Kobayashi, S. et al., JACS, 125, 2989; Denmark, S.E.; Pham, S.M., JOC, 68, 5045; Denmark, S.E.; Heemstra, Jr., J.R., OL, 5, 2303; Romea, P. et al., OL, 5, 519; Rychnovsky, S.D.; Cossrow, J., OL, 5, 2367; Juaristi, E. et al., JOC, 68, 1622; Calter, M.A.; Orr, R.K., TL, 44, 5699; Yamamoto, H. et al., SL, 2219; Gree, R. et al., JOC, 68, 6392; Jha, A.; Dimmock, J.R., CJC, 81, 293; Evans, D.A. et al., JACS, 125, 10893; s e e a l s o : Shibasaki, M. et al., JACS, 125, 5644; Kobayashi, S. et al., CC, 2016; Imashiro, R.; Kuroda, T., JOC, 68, 974; Lang, F. et al., TL, 44, 5285; Mukaiyama, T. et al., CL, 696; Chart, K.-F.; Wong, H.N.C.; EJOC, 83; Yu, C.-M. et al., CC, 2036; Shair, M.D. et al., JACS, 125, 2852; Yanagisawa, A.; Sekiguchi, T., TL, 44, 7163. R~OTMS Pr(OTf)3 OH 0 R-CHO +

R 2~

.L.L

R3

chiral b i s - p y r i d i n o - 1 8 - C r - 6

~ R_ nl.~n2

R3

1 s

53-99% syn:anti = 19-22.4 syn ee = 47-85%

I.A.7.a.1-5 Kwon, O. et al., OL, 5, 1923. TMSO MeO CO2Me

O Me9

~O2Me

CH2C12,-78~ 79% l.A.7.a.l-6 Knight, D.W. et al., CC, 2550. R1

OEt

THF, -78-'20~

1~2,,JDH

60-91% anti:syn = 2-100:1

14


I.A.7.a.l-7 Little, R.D. et al., OL, 5, 3615; Lee, Y.J.; Chan, T.H., CJC, 81, 1406; Mukaiyama, T. et al., BCJ, 76, 813. RO2C CP2TiCI2, Mn RO2O q } a ~---X + R2.CHO R1 THF, rt 2 64-95% I.A.7.a.l-7 Gona, L.-Z.; Wu, Y,-D. et al., JACS, 125, 5262; Martin, H.J.; List, B., SL, 1901; List, B. et al.,AG(E), 42, 2785; Jorgensen, K.A. et al., SL, 1915; Kotsuki, H. et al., SL, 1655; Tanaka, F.; Barbas, III, C.F. et al., OL, 5, 4369; 1685; see also: Ohsawa, A. et al., OL, 5, 4301; Barbas, III, C.F. et al., JOC, 68, 9624; Cordova, A. et al., SL, 1651; Hayashi, Y. et al., JACS, 125, 11208. O OH O e~ "25~ I,~ R~, ~ R-CHO + M Me o Ph Me ~ N H N~"~dIPh H ]OH

12-93% ee = 81-99%

I.A.7.a.l-9 Denmark, S.E.; Beutner, G.L., JACS, 125, 7800. R3 0 T B S OH R3 SiCl4, CH2CI2,-78~ Rj ~ / Y ~ 1 .~ CO2R1 R-CHO + R ~ R 2 OR1 MeO R4 R2 ~ ~ ~ e ~ :

CH2)5

68-97% ee = 10-100:1

l.A.7.a.l-10 Chen, K. et al., JOC, 68, 915; Corma, A.; Garcia, H.; Leyva, A., CC, 2806; Roy, A.K.; Batra, S., S, 2325; Fe!trin, M.P.; Almeida, W.P., SC, 33, 1141; Kataoka, T. et al., JOC, 68, 7532; Krishna, P.R. et al., TL, 44, 4973; Miller, S.J. et al., OL, 5, 3741; Aggarwal, V.K. et al., JOC, 68, 692; Kataoka, T. et al., CEJ, 9, 1496; Basavaiah, D. et al., JOC, 68, 5983; Shi, M. et al., T, 59, 1181; Shi, M., Jiang, Y., JCR(S), 564; Nemoto, H. et al., JACS, 125, 646. OH CO2R1 DARCO,MeCN, rt n~,~_ICO2R1 R-CHO + ~ II " ~ no2c ~,~,,~/-"XN~]..~ / 25-97% n62C -N ~ \ ee = 7-95%


15

I.A.7.a.l-ll Satoh, T. et al., H, 59, 137. TMS~ 1. R-CHO,TBAF,THF, 4AMS~ Ph,,,

2. KOH, M e O H

HO_"!'R ~ _ ~,~

Ph,,,

36-69% l.A.7.a.1-12 Pare, P.W. et al., TA, 14, 971 and TL, 44, 949; Deng, G.-H. et al., HCA, 86, 3510; Li, G.; Headley, A.D. et al., OL, 5, 329; see also; Subburaj, K.; Montgomery, J., JACS, 125, 11210; Huddleston, R.R.; Krische, M.J., OL, 5, 1143. Me

+ R-CHO ~

O

~

Me

Mgl2 OH O . 0~ )b. R ~ I O" CH2C12'

0" tPr

~'I

~Pr 8O-87% de

= 37-58%

l.A.7.a.l-13 Ya, O.W.; Wang, J., OL, 5, 1527. OH Ph-CHO + r CO2Et Zr(OtBu)4,Br2BINOL~ p h ~ C O 2 E t N2 H20/DME, -35~ N2 65% ee = 87%

I.A.7.a.l-14 Mermerian, A.H.; Fu, G.C., JACS, 125, 4050; Long, Y.-Q. et al., JOC, 68, 7555; Ryu, Y.; Scott, AT, TL, 44, 7499. O O OTMS Et20/CH2CI2,rt Me'~~_ )w " RiCo + Ac20 Ph

R R

-'Fe

N

Ph

R,O

Ph

Ph Ph

R

R

73-92% ee = 76-99%

l.A.7.a.1-15 Adrian, Jr., J.C.; Snapper, M.L., JOC, 68, 2143. O R1 O R.NH2 + R1.CHO + ~ R 2 Me2Zn'NiCI(PPh3)3 R ~ N J ~ ~R2 Br CH2C12,rt H 58-97%

16


I.A.7.a.l-16 Donohoe, T.J. et al., OBC, 1, 3749. R

1. LiDBB, BMEA, THF, -78~ 2. Br(CH2)2Br CO2Et ~" I 3. MgBr2.Et2~ Boc 4. R-CHO

COzEt I Boc

68-76% anti:syn = 1.5-20:1 I.A.7.a.l-17 Amii, H.; Uneyama, K. et al., OL, 5, 4297; Ellman, J.A. et al., JACS, 125, 11276; Funabiki, K.; Matsui, M. et al., OL, 5, 2059 and JOC, 68, 2853. TMS~NsPMP BF3oEt20 OH N"PMP ~ + ~TMS CH2C12 "~ R1 F ~ ~ F [ TMS F 40-88% I.A.7.a.l-18 Jacobsen, M.F.; Skrydstrup, T., JOC, 68, 7112. O O ! ! R~OTMS tBu"S~l~ .i. __ EtO2C~ R OR1

Lewisacid ~

tBuIS~lH _ ~A ,,CO2R1 CH2C12,-78"C EtO2C- R ~ R 17-95% dr = 1-32.3:1

I.A.7.a.1-19 Shi, M.; Xu, Y.-M., JOC, 68, 4784. TS~NH O O N"Ts Ar.,J]

i~Ph +

DABCO THF, rt

Ar . ~ ~ P h -

Ph

)Z- o 54-85%

I.A.7.a.1-20 Liotta, D.C. et al., JACS, 125, 3690. O N.,OMe

R"

Jl

+

Ph~NH

S

O

1. TiCI4, sparteine

/e~"

2. Ph-COCI p r ~~

11-51%

S


17

l.A.7.a.1-21 Trost, B.M.; Terrell, L.R., JACS, 125, 338" Jacobsen, E.N. et al., SL, 1919; Jorgensen, K.A. et al., CEJ, 9, 2359; Iqbal, J. et al., JOC, 68, 5735. O R,,N O R"NH A r ~ L A+ O Hu ,,• 4A-MS'THF-"-5~C '~ O ~ ~ ~ 1] "7 chiraldinuclear Zn species Ar x,,~XR1 R1 61-90% dr = 1.7-15:1 ee = 98-99% I.A.7.a.1-22 Ishimaru, K.; Kajima, T., TL, 44, 5441. CO2Me TMSO R1 ipr R O R1 N~ipr T f O H M e O- 2 ~ ~ R-~ 2 + /~~R 2 Et20 H 62-74% de = 70-92%

R.,JI

I.A.7.a.l-23 Jorgensen, K.A. et al., JOC, 68, 2583. R~N,,,.,,.CO2Me R / P G CuCIO, TEA, THF R ~ ~ C O 2 M e "l"

R1

I

~ I~

.~xNz / ~ a9

~

Ar2P

R1R,,~NHPG 61-99% syn:anti = 1.17-19:1 syn ee = 60-97%

I.A.7.a.l-24 Maruoka, K. et al., JACS, 125, 2054. OTMS ~O2 "O'~ + R1-CI-IO "~ g ~ gl chiral quaternary R ammonium bifluoride OH 45-94% anti:syn = 1.32-15.7:1 ee = 11-97% I.A.7.a.1-25 Kobayashi, S. et al., JACS, 125, 2507, 2481. O

O N'~C11H23 R102C,~]

R~__~OSiR3 Cu(OTf)2' CH2C12C11H23" ~ q~,~ H R2

~R3

chiral diamine

O

R102C- R2~R2xR3 77-96% ee = 6-94%

18


I.A.7.a.l-26 Andrews, D.M. et al., S, 1722; Suh, Y.-G. et al., OL, 5, 3635. /Cbz /Cbz Me e ~ : E t 1. BFa.Et20, CH2C12 ~ . ~ Me OEt + ~ ..... Me M TMS 2. K2CO~ EtOH O2Et NHCOCF3 NH2 90%

I.A.7.a.l-27 Estevez, R.J. et al., OL, 5, 4457. OBn BnO 02

aq NaHCO3

BnO"

OH MeOH,rt

O

BnO,

OH

HO"

"~OH OBn

"

53%

I.A.7.a.1-28 Satoh, T., Wakasugi, D., TL, 44, 7517. R2 ]---CN Li,~CN RI~s~ 0 + R CI

Tol

LDA

CN 1 ~

NH2

R 1- X ~ R 55-91%

I.A.7.a.1-29 Kanai, M., Shibasaki, M. et al., OL, 5, 3147. R-CHO+ [,~,CN CuOtBu,dppe H~CN R1 DMSO, rt ~ 1~ "R1 71-95% I.A.7.a.l-30 Katritzky, A.R., et al., JOC, 68, 4932. O R1 CN BuLi,THF,.78oc R'~Bt + p2 or tBuOK, DMSO, rt

O RR~IR~ N 2 71-95%


19

I.A.7.a.2.Addition of N-, P-, S-, Se and Similar Stabilized Carbanions

l.A.7.a.2-1 Norrby, P.-O.; Tanner, D. et al., CCC, 68, 885. N,,R1 RIHN 0 r R.,Jl + "/81"Tol LDA ~ R.~,.., S...Tol Me O 75-98% conversion dr = 1-99:1 l.A.7.a.2-2 Rodrigues, A. et al., S, 1248. O II CI ~P(OEt)2 1. BuLi

O ~_

2. LDA, THF, -780C--,rt I(g./..~

SMe

O P(OEt)2

SMe 55-74%

l.A.7.a.2-3 Ruano, J.L.G.; Aleman, J., OL, 5, 4513. O O II [O II ~STol [,~N- ~'Tol LDA,.78oc ~STolH /O + R ~ fI[ ~ ~ R l ~ " ~ T ~

OTIPS

OTIPS 68-81% de = 98 %

l.A.7.a.2-4 Burger, K. et al., S, 915. O li BuLi N-PG ..P(OEt)2

F3

R

NMe2

PGHN O F 3 R C ~ I I P(OEt)2

THF, -78~

"NMe2 60-75%

l.A.7.a.2.5 Evans, D.A. et al., JACS, 125, 12692; Jorgensen, K.A. et al., OBC, 1, 153. i iOH EtOH, rt R-CHO + Me-NO2 R.~~... NO2

~"r I ~ 1

~

l" .,~"N~ "OAc~ q ~AcO

70-95% ee = 87-94%

20


I.A.7.a.2-6 Huang, P.-Q. et al., OL, 5, 4341.

Et~..r

tBuLi, E +

MeO

%'1~ O

HMPA/THF,-78~

I

O I

PMB

PMB 45-87% de = 4-100%

I.A.7.a.3. Addition of Organometallic and Related Species

l.A.7.a.3-1 Joshi, S.N.; Malhotra, S.V., TA, 14, 1763; Yus, M. et al., TA, 14, 1103; Sprout, C.M.; Seto, C.T., JOC, 68, 7788; Richmond, M.L.; Seto, C.T., JOC, 68, 7505; Bringmann, G. et al, JOC, 68, 6859; Zheng, Z.; Chen, H. et al., TA, 14, 1285; Zheng, Z. et al., TA, 14, 297; Pericas, M.A. et al., JOC, 68, 3110; Wang, R. et al., TA, 14, 659; Braga, A.L. et al., OL, 5, 2635; Pelinski, L. et al., TA, 14, 1701; Ha, D.-C. et al., OL, 5, 4517; Munoz-Muniz, O.; Juaristi, E., JOC, 68, 3781; Soai, K. et al., OBC, 1, 244; Wu, K.-H.; Gau, H.-M., OM, 22, 5193. OH Ph-Me, rt R-CHO + Et2Zn ~ R~Et /oi-i Co

55-77% ee = 72-98%

I.A.7.a.3-2 Shibasaki, M. et al., AG(E), 42, 5489; Garcia, C.; Walsh, P.J., OL, 5, 3641. O iprOH/Ph-Me/Hex, -20~ H ~ . , Me R~'~CO2Me + EteZn 1-19 ~ R" ~"CO2Me 9

Ph

~Bn "/O~HPh

42-95%

ee = 59-96%

I.A.7.a.3-3 Walsh, P.J. et al., JACS, 125, 3210. 120H HO ol

sR Cy2B

~R1 R~

Et2Zn,0~ RV\ /"R 52-86% dr = 1-20:1

CARBON-CARBONBONDFORMINGREACTIONS

21

I.A.7.a.3-4 Ross, N.A.; Bartsch, R.A., JOC, 68, 360; Durandetti, M. et al., OL, 5, 317; Hong, Z.; Xu, X., TL, 44, 489; Colobert, F. et al., OL, 5, 629.

~R

(((.

Br. CO2Et Zn,I 2 0 p I

Ph +

R2

C(R O2Et

Dioxane

1R2 93-99%

I.A.7.a.3-5 Xue, S. et al., SL, 870; Shuto, S. et al.,AG(E), 42, 1021; Yu, M.; Pagenkopf, B.L., OL, 5, 4639; Rayner, C.M. et al., OBC, 1, 834. -

_L

BnO" y

j,,,,o

+

R2Zn

TFA/CH2CI2,0~

BnO'"y"OH

BnO

BnO 45-82%

I.A.7.a.3-6 Joseph, B. et al., SL, 1533; Tobrman, T.; Dvorak, D., OL, 5, 4289; Sugimoto, O.; Yamada, S.; Tanji, K.; JOC, 68, 2054; see also: Hilmersson, G. et al., TA, 14, 439; Chemla, F. et al., JOC, 68, 9747; Hoffmann, R.W. et al., JOC 44, 4546; Liu, Y.; McWhorter, Jr., W.W.; JOC, 68, 2618; Hakansson, M. et al., CEJ, 9, 4678; Nakada, M. et al., JACS, 125, 1140; Evans, W.J. et al. OL, 5, 2041; Sakamoto, M. et al., JOC, 68, 942; see also: Oi, S.; Inoue, Y. et al., T, 59, 4351. OHC ~ ~ ~ + I BuLi ~ ~ O ~ THF, -78C EtJ

Boc

Et2

~N~~ Boc 73%

I.A.7.a.3-7 North, M. et al., OL, 5, 4505; North, M., TA, 14, 147; Najera, C.; Saa, J.M. et al.,AG(E), 42, 3143; Deng, L. et al., JACS, 125, 9900; Feng, X. et al., SL, 558; Azizi, N.; Saidi, M.R., JOM, 688, 283; Fossey, J.S.; Richards, C.J., TL, 44, 8773; Cordoba, R.; Plumet, J., TL, 44, 6157. [(salen)TiO]2, -400C EtO2C~../CN R-CHO + EtO2C-CN ~ [

R 23-95% ee = 76-99%

22


l.A.7.a.3-8 Mangeney, P. et al., OL, 5, 2567. NBn2 1. SBuLi,THF, -80--+-40"C TMS ~ / 2. CuCN, LiCI, -800C 3. R-CHO

TMS

..... pNBn2 I-I0 65-88%

l.A.7.a.3.9 Billard, T.; Langlois, B.R. et al., AG(E), 42, 3133 and SL, 230, 233; Langlois, B.R. et al., TL, 44, 1055; Prakash, G.K.S. et al., OL, 5, 3253; Caron, S. et al., S, 1693. Mg. JPh 1. CsF, DME OH or TBAT, THF ~ 1 - ~RR/- CF3 ~ § S 2. Bu4NF Fa~ 0 ee

30-93%

I.A.7.a.3-10 Prakash, G.K.S. et al., AG(E), 42, 5216. OH OH ~,R-CHO

+ PhSO2CF2H

tBuOK

DMF, -50~

RF~~~

R

52-82% de - 86-94 %

l.A.7.a.3-11 Kubota, K.; Leighton, J.L., AG(E), 42, 946; Hayashi, T. et al., JOC, 68, 6329; Malkov, A.V.; Kocovsky, P. et al., AG(E), 42, 3564; Maruoka, K. et al., CEJ, 9, 4380; Huckins, J.R.; Rychnovsky, S.D.; JOC, 68, 10135; Hsung, R.P. et al., SL, 791; Massa, A. et al., TL, 44, 7179; Zheng, X., Zhang, Y., JCR(S), 472; Oriyama, T. et al., OL, 5, 3045; Rowlands, G.J.; Barnes, W.K., CC, 2712; Denmark, S.E.; Fu, J., CC, 167; see also: Lloyd-Jones, G.C. et al., CCC 68, 865; La Ronde, F.J.; Brook, M.A., CJC, 81, 1206; Inanaga, J. et al., TL, 44, 8765; Leitch, S.K.; McCluskey, A., SL, 699; Zhang, Y. et al., JCR(S), 438. /---4-BrPh OH R-CHO + ~ .~~~~ K,,,,,,~,.,o~ "CI CH2C12,-10oc K

~-- 4-BrPh

~

61-93% ee = 95-98 %

I.A.7.a.3-12 Ollevier, T.; Ba, T., TL, 44, 9003. 1. R1-NH2, Bi(OTf)3.nH20 R-CHO

2. CH2=CHCH2-TMS

HN..R 1

27-86%


23

I.A.7.a.3-13 Fernandez-Zertuche, M.; Ordonez, M. et al., TA, 14, 2693; Goti, A.; Merino, P. et al., OL, 5, 4235. R

~

O . .. ~p~

Nc~OH ~ ~0 Et2AICN,ZnBr2 ~- R'- _.~1 " , ~ O Ph-Me, -780C ~p~ 27-82% dr = 15.7-49:1

l.A.7.a.3-14 Morgan, J.B.; Morken, J.P., OL, 5, 2573; Yoshimitsu, T.; Arano, Y.; Nagaoka, H., JOC, 68, 625. R~ Me + [ EtO2G., 2 jO, r~_2 1. Pt(dba)2,PCy Hqk 1~. /Me EtO2C

tJB

2. R1-CHO "~ 3. H202,NaOH

I.A.7.a.3-15 Krische, M.J. et al., JOC, 68, 11. O o R ~ R1 THF,25~ R& n

~oO, n

R((

OH 58-72% ee = 33-74%

H~,,,R1

L~,,~J )n 5-91% syn:anti = 99:1

I.A.7.a.3-16 Gosmini, C. et al., S, 1909; Durandetti, M. et al., JOC, 68, 3121; Inomata, K. et al., H, 60, 2743; Auge, J. et al., JOM, 679, 79; Nair, V. et al., S, 2542. OH R~R10 + ~,,,,~OAc Zn'CoBr2 ~ R~ TFA/MeCN,rt 40-96% I.A.7.a.3-17 Malkov, A.V.; Kocovsky, P. et al., JOC, 68, 9659; Yamamoto, H. et al., JOC, 68, 5593; Chemler, S.R.; Roush, W.R., JOC, 68, 1319. OH MeCN, -40~ r ~ A Ar-CHO + R ~ S n C I 3 RR -'_ 27-88% ee = 87-99%

24


I.A.7.a.3-18 Thomas, E.J. et al., CC, 1460. BuSn / ~ ~ BiI3 R-CHO + OBn

R

OH ~

Me

OBn

Me 45-92% 9-15:1

I.A.7.a.3-19 Lombardo, M.; Morganti, S.; Trombini, C., JOC, 68, 997; Lombardo, M.; Trombini, C., et al., CC, 1762; Berkessel, A. et al., AG(E), 42, 1032; Suzuki, H. et al., OBC, 1, 2160. O Br OH

1 ~ . o ~ ~ " ' 1 in TH~ or Zn ~H~, H~O. R~~'*'r~

R-CHO +

R

2. K2CO3

OH 60-94% syn:anti = 4-5.7:1

I.A.7.a.3-20 Thadani, A.N.; Batey, R.A., TL, 44, 8051; see also: Hall, D.G., JACS, 125, 10160; Yakelis, N.A.; Roush, W.R., JOC, 68, 3838; Szabo, K.J. et al., OL, 5, 3065. TBSO OH W ! TBSO

R2

Bu4NI

R

~ .I.

R~ C H O

+

R ~ . B F 3K+ CH2CI2/H20

TBSO

A~

OH

94-97% 1:1.86-3 I.A.7.a.3-21 Grigg, R. et al., TL, 44, 7969. II Ar-I + ~

+ R1-CHO

Pd(OAc)2, In, Cul TFP

A

R1 R

R

50-78% I.A.7.a.3-22 Nokami, J. et al., AG(E), 42, 1273. R1 ipr Ts-OH.H20

R-CHO + Me

R1 61-96% ee = 99%


25

I.A.7.a.3-23 Parsons, P.J. et al., SL, 861" Gallagher, E.T.; Grayson, D.H., OBC, 1, 1374. Br OH TMS TMS tBuLi,ZnCI2 R ~ R-CHO + .78~

~

41-90%

dr = 1.5-9:1 l.A.7.a.3-24 Miller, M.J. et al., JOC, 68, 139. R1 O R-CHO,Pd(OAc)2,PPh~ I n I H20/TI-IF

oR1 O 39-73% cis:trans = 1:13-100

I.A.7.a.3-25 Yu, C.-M. et al., TL, 44, 5487; Loh, T.-P. et al., TL, 44, 507. BINOL-Ti[(OCH(CF3)2 FG~R-'CHO + ~ FG,, H R ~ tBuSBEt2,Ph-CF3, "20~ SnBu4 54-83% ee = 84-96% I.A.7.a.3-26 Urabe, H.; Sato, F. et al., JACS, 125, 6074. TMS tBuO2~

-l- R-CHO Ti(Oipr)4,..iprMgCI ~ I~,"~-~"R~r ~co2tBu ..... Et20' "20~ C6H13

HOTM~ ~-C6H13 61-77% ds = 7.33-13.3:1

I.A.7.a.3-27 Ramachandran, P.V. et al., JOC, 68, 9310; Concellon, J.M. et al., CEJ, 9, 5343; see also: Roy, A.K.; Batra, S., S, 1347; Verkade, J.G. et al., AG(E), 42, 5054; Almeida, W.P.; Coelho, F., TL, 44, 937; Krishna, P.R. et al., SL, 888; McDougal, N.T.; Schaus, S.E., JACS, 125, 12094. R2 OH iBu2AI- .,CO2Et R~~,ICO2Et CO2Et DIBALH,NMO "~ + R~OR. rt L R ~ ] THF, 0~ ~R THF, R 70-96%

26


I.A.7.a.3-28 Jeong, I.H. et al., TL, 44, 7213.

F3%

R1

TM~O (OMe F3C ~

Q~R 1 +

Ph Me

TBAF

R

Et20,-15~ 72-99%

I.A.7.a.3-29 Novikov, Y.Y.; Sampson, P., OL, 5, 2263; Shen, Y.; Wang, G., S 209. J Br

BuLi + O~R 1 .~- \ \ R TI-IF, -110~ B/

x( OH R1 R

20-85%

I.A.7.a.3-30 Jamison, T.F. et al., JACS, 125, 3442; Colby, E.A.; Jamison, T.F., JOC, 68, 156. R - ' - - R1 + R2.CHO

Ni(cod)~ Et3B, DMI/EtOAc iPrli, (

~,a Me

Ph2~'

OH Z. R2

R_ R1

35"97%

ee - 42-96%

I.A.7.a.3-31 Toru, T. et al., JOC, 68, 5766; Johnson, II, D.C.; Widlanski, T.S., JOC, 68, 5300. Tol

+ R1.CO2Et 1. LDA, THF,-780C ~ 2. DIBAL, TItF, -78~ ~TMS

O.. % 9 H T~ R1 ~TMS 30-83% dr = __.98:0:0:0

I.A.7.a.3-32 Shibasaki, M. et al., JACS, 125, 5634; Seki, M. et al., S, 2311; Bernardi, L.; Ricci, A. et al., SL, 1778; Heydari, A. et al., S, 1962; Hou, X.-L. et al., JOC, 68, 6264; ~ R N,,O TMS-CN,Gd(Oipr)3, EtCN Ph2 ~ r ~.. Ph2P~.O "OH

o ~ OH

~

Ns ~i~pph2 R~ R1 0 58-99% ee = 51-98%


27

I.A.7.a.3-33 Wipf, P.; Stephenson, C.R.J., OL, 5, 2449; Chan, A.S.C. et al., JOC, 68, 1589. 1. Cp2ZrHCI, CH2C12,rt Nil 2. Me2Zn, Ph-Me, -78-,0~ ~fCO2 R1

R

~ R,,,~.,,,,-~ R1

3. o~,,co~1

75-93%

R1

LA.7.a.3-34 Marshall, J.A.; Bourbeau, M.P., OL, 5, 3197; Wang, R. et al., AG(E), 42, 5747; Kamble, R.M.; Singh, V.K., TL, 44, 5347; Cozzi, P.G.; AG(E), 42, 2895; Chan, A.S.C. et al., AG(E), 42, 5057; Chan, W.L.; Chan, A.S.C. et al., TA, 14, 449; Gong, L.-Z.; Jiang, Y.-G. et al., JOC, 68, 7921; Ishikawa, T.; Saito, S. et al., JOC, 68, 3702; Garcia-Tellado, F. et al., CEJ, 9, 3122; Bittman, R. et al., JOC, 68, 348,355.

Me

TMS 67% syn:anti = 19:1

l.A.7.a.3-35 Isobe, M. et al., OL, 5, 4883; Saeeng, R.; Isobe, M. et al., TL, 44, 6211; Yadav, J.S. et al., S, 247.

A~A~.~

+ [

SnCl4 MeCN, 0~

TMS

AcO

AcO" 78%

I.A.7.a.3-36 Florjancic, A.S.; Sheppard, G.S., S, 1653. H O Boc~N,,,jCO2H 1. Ar-Li, Et20 ~ H C I . H 2 ~ ~ A

R

2. HCl/dioxane

r 12-63%

ee = 99% l.A.7.a.3-37 Wang, X.; Zhang, Y., T, 59, 4201; Zhang, Y. et al., TL, 44, 1667.

R~O Bt

SmI2 ~

~_~

THF,rt 0-96%

28


l.A.7.a.3.38 Dieter, R.K. et al., T, 59, 1083; Frey, L.F. et al., T, 59, 6363. R R 1. SBuLi, CuX'2LiCI R R

I

2. R1-COCI

Boc

Boc

O

18-99%

LA.7.a.3-39 Gosmini, C. et al., T, 59, 8199; Wang, D.; Zhang, Z., OL, 5, 4645; s e e also: Kawakami, J. et al., S, 677; Vaquero, J.J.; Ezquerra, J. et al., OL, 5, 3791. /~___ CoBr2 /~_._~~ Z n B r + R-COCI F F 47-67% l.A.7.a.3-40 Zhang, Z. et al., JOC, 68, 10172; MaGee, D.I. et al., TA, 14, 3177; s e e also: Koutek, B. et al., SL, 937. O O R ~ + C I ' ~ ""I~Z CuI, TEA ~ _ ~ , ~ . . Z THF, rt O 43-95%

R rO

I.A.7.a.3-41 Boezio, A.A.; Charette, A.B., JACS, 125, 1692; Tomioka, K. et al., JOC, 68, 9723; Wang, C.-J.; Shi, M., JOC, 68, 6229; Gong, L.Z.; Mi, A.-Q. et al., JOC, 68, 4322; see also: Palmieri, C. et al., JOC, 68, 1200; Alexakis, A. et al., TL, 44, 8893; Martelli, G.; Savoia, D., CCC, 68, 1531; Charette, A.B. et al., JOC, 68, 3241; Trehan, S. et al., CC, 1420; s e e also: Galvez, J.A. et al., EJOC, 2268; Leault, C.; Charette, A.B., JACS, 125, 6360.

l~N",PPh2 II O

+ R12Zn

c.,o,02 =e OuP-OS~ R; Ph-Me, 0*C

H

,o Ph2

51-98% ee = 8 5 - 9 6 %

I.A.7.a.3-42 Motoyama, Y.; Nishiyama, H., SL, 1883; Maruoka, K. et al., TA, 14, 1603; Szabo, K.J. et al., AG(E), 42, 3656; Masuyama, Y. et al., TL, 44, 2845; Dias, L.C. et al., TL, 44, 6861. R1 ~HR~ R1 (ipr-Phebox)RhCl2(H20) R-CHO + ,~ ~'SnBu3 4A MS, CH2CI~ rt 82-97% ee = 9 0 - 9 9 %


29

l.A.7.a.3-43 Evans, J.W.; Ellman, J.A., JOC, 68, 9948; Garcia Ruano, T.L. et al., OL, 5, 677. tBu tBu I

I

~o

H~'O

Me.

Ph-Me or THF, -78~ OPG

Me

R

OPG 72-98% syn:anti = 1:49-11.5:1

I.A.7.a.3-44 Wipf, P. et al., JACS, 125, 761; Minami, T. et al., JOC, 68, 4947. R2 N

Cp2ZrHCl, Me2Zn

R2~NH R1 35-90%

l.A.7.a.3-45 Kobayashi, S. et al., JACS, 125, 6610 and SL, 1749 and AG(E), 42, 3927; Takemoto, Y. et al., JOC, 68, 6745; Leighton, J.L. et al., JACS, 125, 9596; Niwa, Y.; Shimizu, M., JACS, 125, 3720; see also: Ricci, A. et al., JOC, 68, 3348; Crousse, B.; Bonnet-Delpon, D. et al., JOC, 68, 6444. H N'N"Bz

I1

+

CH2C12, -78~ SiCI3 ' ToI,~s,,Me t O

~

RI

H HN,,N,,B z 61-95% ee = 70-98 %

l.A.7.a.3.46 Hirashita, T. et al., JOC, 68, 1309. N,,R2 __~J

-I- B r ~ I

R1

R

HN,'R2 1. In, DMI _~ R l ~ R 3 2. R3-X, Pd(PPh3)4, LiC! R

22-77%

I.A.7.a.3-47 Trost, B.M.; Jonasson, C., AG(E), 42, 2063. OH P h ~

~e

MeO2C~N +

VO(OSiPh3)3 ~

LA r CH2CI2' 35.45~ -

O HN"CO2Me P h ~ A r Me 40-85% anti:syn = 1.5-9:1

30


l.A.7.a.3-48 Hoveyda, A.H.; Snapper, M.L. et al., OL, 5, 3273 and AG(E), 42, 4244; Knochel, P. et al., AG(E), 42, 5763; see also: Jiang, B.; Si, Y.-G., TL, 44, 6767; Vallee, Y. et al., TA, 14, 525; Wei, C.; Li, C.-J., JACS, 125, 9584; Li, C.-J. et al., OL, 5, 4473. Zn(CEC-TMS)2,Zr(Oipr)4

Me~

Zn(CH2TMS)2'Ph-Me' Ort/p'~ r MH~

RJ '

III1~ 2

~ ~ph TM

R ~ TMS 69-90% ee = 69-86%

I.A.7.a.3-49 Dransfield, P.J.; Shipman, M. et al., OBC, 1, 2723; Andrade, Z. et al., SL, 1189; Amat, M.; Bosch, J. et al. TA, 14, 1679; Dondoni, A.; Perrone, D., T, 59, 4261. OAe OAc Nuc, BF3.Et20 ~.,,,OAc OAc CH2C12,rt Nuc~A~N~k~I OAc I

I

Fmoc

Fmoc 63-80%

I.A.7.a.3-50 Shibasaki, M. et al., JACS, 125, 4712. O

O

N"PPh2 Ar'~[

+

OMe

0.,55

O

Et2Zn, THF, 3A MS ~

m

I

o ~

e Ar~

~

~ N ~ - - ~ 1 7 6

. A'~H [ ~ ~

96-99% anti:syn = 3-49:1 ee = 98-99%

I.A.7.a.3-51 Hatakeyama, S. et al., OL, 5, 3103; Shi, M.; Chen, L.-H., CC, 1310. N,,R ~ , ~ .CF3 DMF,-55~ ~ H~f" R O CF3

OH

CF3

Ar

- 1] ~~,~~E D'-t~'_ o

32-57% ee

= 93-100%


31

I.A.7.a.3-52 Nakagawa, M. et al., JOC, 68, 3112. N,,R

R1 Yb(OTf)3,TMS.CI R2

THF/CH2CI2,rt

R"NH i11R1 111 A r ~ R 2 24-92%

l.A.7.a.4 Other 1,2-Additions I.A.7.a.4-1 Rick, R.T.; Jacobsen, E.N.,AG(E), 42, 4771; Ding, K. et al., AG(E), 42, 5478; Aikawa, K.; Mikami, K., AG(E), 42, 5458; Yang, D. et al., OL, 5, 3749; Yamada, T. et al., BCJ, 76, 49; Sasai, H. et al., OL, 5, 2647. OTMS DIPEA,4A MS, 40C OH OTMS R-CHO + ~ .1~ R ~ Me ~ 47-90% OTIPS 'tN~'~ ee = 87-93% "o-C%~

cl ~ "T tBu

l.A.7.a.4-2 Uneyama, K. et al., CC, 1752; see also: Namy, J.-L. et al. TL, 44, 5507. N"Ar CO, Pd2(dba)3.CHCI~K2CO3 Ar--~~___~--Ar

I

DMF/Ph-Me, 70~

Rf

Rf

0-82% I.A.7.a.4-3 Yamago, S.; Yoshida, J. et al., AG(E), 42, 117. R2

N"R2

(EtO)3Si-TePh

R,~R1 + R3--~

~

HN'

/TePh

R)

~__R3

R1 43-93%

I.A.7.a.4-4 Xu, B.; Shi, M., SL, 1639; Li, C.-Q.; Shi, M., OL, 5, 4273; Krische, M.J. et al., JACS, 125, 11488; Yu, C.-M. et al., OL, 5, 2813. Ph t

.

O~CO2Et CO2Et

Yb(OTf)3 ~ AcCI, rt

Phil OAc ~ICO2E CI CO2Et 85%

t

32


I.A.7.a.4-5 Denmark, S.E.; Fan, Y., JACS, 125, 7825; Chen, J.; Cunico, R.F., TL, 44, 8025. OH R-NfC + R1-CHO + SiCl4

~

q

~

R"

R1

er = 2-99:1 ~,a,'J~

Me .J 2

I.A.7.a.4-6 Demir, A.S. et al., OL, 5, 2047. O Benzaldehyde lyase ._ l [ MgSO4,KH2PO4 buffer A r ~ O M e OH 70-94% ee = 91-98%

Ar-CHO + O H C ~ O M e

I.A.7.a.4-7 Procter, D.J. et al., OL, 5, 4811; Py, S.; Vallee, Y. et al., SL, 1527; Holemann, A.; Reissig, H.-U., OL, 5, 1463; Mukaiyama, T. et al., BCJ, 76, 413.

Mg

Me"~ O

Sml2 71% O ~MeOIt/THF

Sml2

,.e

~..

O tBuOH/THF

\OH O

64% I.A.7.a.4-8 Mead, K.T. et al., TL, 44, 6351, 6355. Ph TiCl4 Ph-OTIPS +

Ph n

CH2C12, -780C

H TIPSO" ~ "

82%

I.A.7.a.4-9 Najera, C.; Saa, J.M. et al., TA, 14, 197. CN aminomethyl BINOL R ~ o ~ C O 2 M e R-CHO + NC-CO2Me ~'95-98% ee = 1-10:1


33

I.A.7.a.4-10 Kalbalka, G.W. et al., TL, 44, 1187. OH CI Ar-CHO +

R

PhBCI2 Ar ~ CH2CI2

R 36-96% anti = 64-98%

I.A.7.a.4-11 Wei, X.; Taylor, R.J.K., TL, 44, 7143. "~R 1

R-Li ~. ~ Et20, rt "-

Ph2

R1 R

Ph2 62-81%

I.A.7.a.4-12 Freistad, G.K. et al., AG(E), 42, 4982; Naito, T. et al., CC, 426. ~ ~ R-I,Cu(OTf)3,Et3B, 0 2 ~ ~ ~

~u

~.~ R~j

H

~o-~~o

R'~R 1 44-88% ee = 81-95%

l.A.7.a.4-13 Suzuki, K. et al., JACS, 125, 8432. O--N .-- R I ~ O R ~ ~~. ~

~O"N! RQ

R

DBU, tBuOH, 40~ OH Me

~S

~Et

~Br"

R2 / ~ , r ~

HO O 79-96%

I.A.7.b Conjugate Additions

I.A.7.b.1 Enolate-Type Carbanions I.A.7.b.l-1 Kaneda, K. et al., JACS, 125, 10486; Narasimhan, S. et al., TA, 14, 113; Akiyama, T. et al., CC, 1734; Shimizu, K. et al., TL, 44, 7421; Kozlowski, M.C. et al., JOC, 68, 1973. "A Novel Montmorillonite-Enwrapped Scandium as a Heterogeneous Catalyst for Michael Reaction"

34


I.A.7.b.l-2 Shibasaki, M. et al., JACS, 125, 2582; Alexakis, A. et al., OL, 5, 2559; Maruoka, K. et al., JACS, 125, 9022; Keller, L.; Dumas, F.; d'Angelo, J., EJOC, 2488; Melchiorre, P.; Jorgensen, K.A., JOC, 68, 4151; Miura, K.; Hosomi, A. et al., SL, 2068; Sivaram, S. et al., TL, 44, 6047; Verkade, J.G. et al., T, 59, 561; Harada, T. et al., JOC, 68, 10046; Hagiwara, H. et al., OS, 80, 195; Willis, C.L. et al., TL, 44, 8153. O OMe O R1 O OMe

o. t2zn , s THF, -20~

linked BINOL

39-99% 1.56-13.3:1

I.A.7.b.l-3 Takemoto, Y. et al., JACS, 125, 12672; Taylor, M.S.; Jacobsen, E.N., JACS, 125, 11204; Ikariya, T. et al., JACS, 125, 7508; Jorgensen, K.A. et al., JOC, 68, 5067; Kanemasa, S. et al., TA, 14, 635; Grossman, R.B. et al., JOC, 68, 871; Labadie, G.R. et al., HCA, 86, 2741; Nakajima, M. et al., T, 59, 7307. R1

R1 ~g20 2C ~ v

Ph-Me, rt

R202C.~CO2R2 "1" R ~ N O 2

H

v3~N~s

H

~Me2

~

R~-,

CO2R2 "NO2

74-95%

ee = 81-93%

cv3

I.A.7.b.l-4 MacMillan, D.W.C. et al., JACS, 125, 1192; see also: Langer, P. et al., TL, 44, 7921. TMSO~~R

+ M~CHO

DNBA ~ o @ R o

-

P

"7"

"CliO

q~

n

73-87% 24-1:1-7 syn:anti = 90-98%

l.A.7.b.l-5 Beak, P. et al., OL, 5, 4155. I~ .,R 1

NC~R1 CN

BuLi, sparteine ~

+ ArtN"B~

Ph-Me, -78~

N

~

CN R Ar~N..Boc 86-96%

dr = 1.2-4:1 er = 6.7-19:1


35

I.A.7.b.l-6 Kerr, M.S.; Rovis, T., SL, 1934. o EWG ~

/

OH EWG

KHMDS,Ph-Me '"

~l~

N ~S~ BE'4

58-90% ee = 75-95%

Ph

I.A.7.b.l-7 Satoh, T. et al., T, 59, 4327; Loughlin, W.A.; McCleary, M.A.,OBC, l, 1347. ( ~ ~ S TIo l D ~...R 1

+ LiCH2CO2R2

TI-IFI~

:-'~"STol

O

~.R

1

O 0-99%

I.A.7.b.l-8 Cao, S. et al., M, 134, 529. R102C~

O2~S~._CO2R+

~CO2

!.A.7.b.20rganometallic and Related Reeagents I.A.7.b.2-1 Hird, A.W.; Hoveyda, A.H., AG(E), 42, 1276. O 1 O R12Zn, (CuOTf)2Ph Meti: ~,OtBu ii

i

t~ppb2

N H

ii

NHBu

R•oO

61-95% ee = 76-98%

O ~Pr

I.A.7.b.2-2 Sosnovskikh, V.Y. et al., JOC, 68, 7747. O R1

R1

K2CO3'TEBA 02 N--~-'/~--"~ CO2R1 DMF ~"~CO2R 70-84%

N

+ TMS-CF3

THF, -10~

~"

O R1

R

50-86%

36


I.A.7.b.2-3 Krauss, I.J.; Leighton, J.L., OL, 5, 3201; Feringa, B.L. et al., JACS, 125, 3700; Fraser, P.K.; Woodward, S., CEJ, 9, 776; Zhou, Q.-L. et al., JOC, 68, 1582; Hu, X. et al., JOC, 68, 4542, 8277; see also: Casamitjana, N. et al., JOC, 68, 9541; Zhu, N.; Hall, D.G., JOC, 68, 6066; Suarez, R.M.; Sestelo, J.P.; Sarandeses, L.A., CEJ, 9, 4179; Fleming, F.F. et al., JOC, 68, 4235; Chan, A.S.C. et al., TL, 44, 7217; Dambacher, J.; Bergdahl, M., CC, 144; Fleming, F.F. et al., T, 59, 5585; de Oliveira, A.R.M. et al., SL, 975; Lee, P.H. et al., S, 2189; Bergbreiter, D.E.; Li, C., OL, 5, 2445; Ma, S. et al., JOC, 68, 8996; Pearson, A.J.; Kim, J.B., OL, 5, 2457; Wendisch, V. et al., TA, 14, 3095; Tsantali, G.G.; Takakis, I.M., JOC, 68, 6455; Quntar, A.A.A.; Srebnik, M., CC, 58; Ohe, T.; Uemura, S., BCJ, 76, 1423. Cu(OTf)2, CH2C12,rt R12Zn +

IY~

)n

Ph2

)n

_,"

R F'

9u

R R 58-90% ee = 84-97 %

I.A.7.b.2-4 Dambacher, J.; Bergdahl, M., OL, 5, 3539; Williams, D.R. et al., CC, 2220; Arai, Y. et al., S, 1511; Murthy, K.S.K.; Rey, A.W. et al., TL, 44, 5355. .Bu

Me~

M

/~)

Li(BuCul) ,Ph 9 ~ Et20, -78~

\

O~~"

~

Li(BuCuI)

O~~

,Ph TMS-I ~ e THF,-780C

90% 15.7:1

\ O~~"

,Ph

I d r 83% 49:1

I.A.7.b.2-5 Knopfel, T.F.; Carreira, E.M., JACS, 125, 6054; Carreira, E.M. et al., OL, 5, 4557. Ar

+

Cu(OAc)2, Na-ascorbate H20[BuOH, rt A

55-98%

l.A.7.b.2-6 Ogle, C.A. et al., TA, 14, 3281; Iuliano, A.; Scafato, P., TA, 14, 611. "Chiral Lithiothiophenes as Non-Transferable Ligands in Organocuprate Conjugate Addition Reactions."


37

I.A.7.b.2-7 Xie, M.; Huang, X., SL, 477. 1. PhMgBr, CuCN, THF/CH2CI2, -20~ R .SO2R1 R SO2R1 ~" h/~ - ( E, 2. E + p 56-82% I.A.7.b.2-8 Miyaura, N. et al., SL, 1040 and AG(E), 42, 2768; Andrus, M.B. et al.,AG(E), 42, 5871; Li, X.; Chan, A.S.C. et al., TL, 44, 6505; Boiteau, J.-G.; Minnaard, A.J.; Feringa, B.L., JOC, 68, 9481; Feringa, B.L. et al., OL, 5, 681; Adapa, S.R. et al., TL, 44, 5115; see also: Oi, S.; Inoue, Y. et al., OL, 5, 97. Rh(acac)(C2H4)2, KOH H20/dioxane, 50~ ~ ArR ~ ~ O R2 Ar-B(OH)2 4- R R ~ O R2 P--NR2

38-97% ee = 31-99%

I.A.7.b.2-9 Fleming, F.F. et al., JOC, 68, 7646. CN

M

CI

CN tBuMgCI

R 54-75%

I.A.7.b.2-10 Chemla, F. et al., AG(E), 42, 4043.

//

BnN/ _~CO2Me + Bu2Zn

\\

I2 ~

Bn~ C OI1 2_

Me

~Bu 48%

I.A.7.b.2-11 Krische, M.J. et al., JACS, 125, 1110; Procter, D.J. et al.,

JOC, 68, 3190. M

,o

e--Ci e O

[Rh(cod)Cl]2, BINAP "~F--~,,OH + Ph-B(OH)2 ~" p h ~ ~ ) n 69-88%

dr = 19:1 ee = 94-95%

38


l.A.7.b.2-12 Py, S.; Vallee, Y. et al., AG(E), 42, 2265; Lassaletta, J.M. et al., JOC, 68, 2698. R1 R1 "O'N+~'~,~R2 SmI2 HO'N~R2 R[~ + ~ I C O 2 Et ~ R~,1, ~ H20/THF, -78~ CO2Et 36-96% dr = 1.3-19:1 I.A.7.b.2-13 Lee, P.H. et al., JOC, 68, 2510. o EtO2~y

R~~]

o

'~R1 In, TMS-CI~

EtO2C

THF, rt

~

R1

EtO2y~~

R2

r

t

~

80-97% I.A.7.b.3. Other Conjugate Additions I.A.7.b.3-1 Jorgensen, K.A. et al., AG(E), 42, 661, 4955. BnO2.C O R O BnO2C~ + R ~ R 1 neat, rt ~ B n O 2 ~ R 1 Bn~__.~ BnO2C 33-99% r~NMe ee = 59-99% COzH I.A.7.b.3-2 Furman, B.; Dziedzic, M., TL, 44, 6629.

o

TM

- C I:1U

THF, 30~ R

k

56-84% l.A.7.b.3-3 Iwasawa, N.; Lee, P.H. et al., JACS, 125, 9682. O OTBS + R-X

Me2S, TBS-OTf, In THF, -780C

~"

R 60-74%


39

I.A.7.b.3-4 Venkateswarlu, Y. et al., TL, 44, 6257; Ji, S.-J.; Loh, T.-P. et al., SL, 2377; Bandini, M.; Umani-Ronchi, A. et al., S, 397 and TL, 44, 5843; Marcantoni, E. et al., JOC, 68, 4594. ~_~RIR~R3

O ~2/~R3 + R

H

Bi(OTf)3 MeCN.rt-

H 80-95%

I.A.7.b.3-5 Sammis, G.M.; Jacobsen, E.N., JACS, 125, 4442. O O BZ'H~

+ TMS-CN

iPrOH/Ph-Me,rt I. B z , ~

~R

tBu

~u

-u~OxClo-~ ~___

'~

___j

R 70-96% ee = 87-98 %

I.A.7.b.3-6 Sibi, M.P. et al.,AG(E), 42, 4521; Takasu, K.; Ihara, M. et al., OL, 5, 3017. O O O. O R1 ( ~ ~ O R + RI-x _______~__~Et3B/O2'Bu3SnH-78C ~ N'~~~'~ THF/CH~Cb,, ~ OR 70-92% ~lN~Ni ~~ ee = 50-92% tBu

O MeO2C--'~H~~~-Me TBSp.=

CO2Me TBS(~L ~ I ~ A Me,.,~.~~j.~H v TBSd ~/'~ -Me

tBu

"r

PMe3 H20/THF TBSO FI 84%

dr = 6:1

-Me

40


I.A.7.b.3-8 Skrydstrup, T. et al., JACS, 125, 4030; Riber, D.; Skrydstrup, T., OL, 5, 229; Fuchibe, K.; Iwasawa, N., CEJ, 9, 905; see also: Pan, X. et al., JCR(S), 559; Yadav, J.S. et al., TL, 44, 8959. R1 R1 O N~S~~N ~ SmIz ~ RH + X THF,-78~ RH X O ~{2 O R~ 28-90% I.A.7.b.3-9 Fadini, L.; Togni, A., CC, 30.

X

NH +

lWO

R R1 ~-( [Ni(ppp)(THF)]CIO4 ~. EWG THF, rt

62-99% I.A.7.b.3-10 Kataoka, T. et al., AG(E), 42, 2889.

CHO

S N ~/

LO_~ / ph/

Ph

~Me

+

~

ff.....~ / O ? . ~ p h ~ _ ~ _ R _ ~ N ~ Me

BF3~t 2 0 CH2C12

R

Ph u 27-93% dr = 2.2-100:1

I.A.8. Other Carbon-Carbon Single Bond Forming Reactions

I.A.8-1 Murahashi, S. et al., JACS, 125, 15312.

Ar-NMe2

RuCI3onH20,NaCN,02 AcOH/MeOH

ME

Ar--~C N 81-88%

I.A.8-20uvry, G.; Zard, S.Z., SL, 1627; Gagosz, F.; Zard, S.E., OL, 5, 2655; Zard, S.Z. et al., CC, 204 and SL, 382; Nagano, H. et al., TL, 44, 7027; Naito, T. et al., OBC, 1,381; Yao, C.-F. et al., CEJ, 9, 2123; see also: Parsons, A.F. et al., OBC, 1, 373.

Ar

laurel peroxide

R,,

OEt +

R1 Ar

DCE,reflux ~

R1 33-64%


41

I.A.8-3 Joshi, N.N. et al., JOC, 68, 5668; Li, Y. et al., JOM, 687, 12; Nishino, T.; Nishiyama, Y.; Sonoda, N. BCJ, 76, 536; Shimizu, M. et al., SL, 1535. OH Zn, TMS-CI,MeCN, -10~ 1 . Ar Ar-CHO '~ A

o,,k/.o-

o-

~.~"N--__~

65-94% dl:meso = 8-100:1 ee = 50-96%

I.A.8-4 Kim, S. et al., JACS, 125, 9574; Oltra, J.E. et al., OL, 5, 1935; Curran, D.P. et al., OL, 5, 419; Kozikowski, A.R. et al., JMC, 46, 921. l

~CO2Et

.CO2Et /~ ~CO2Et EtO2C~~-'-~ EtO2C d

(Me3Sn)2 Ph-H ~ (~P(OEt)2

EtO2C~co2Et

(other examples given)

79%

I.A.8-5 Renaud, P. et al., AG(E), 42, 4230; Landais, Y.; Renaud, P. et al., T, 59, 8543. OMe DMe O ~ I R

Bu3SnH,NaBH3CN ~ tBuOH' 80oc

H ~ R

R

Me R

44-81% dr = 5.25-15.7:1

I.A.8-6 Aggarwal, V.K. et al., OL, 5, 5075; Trauner, D. et al., OL, 5, 4931; Tius, M.A. et al., OL, 5, 4927; Fernandez-Mateos, SA. et al., JOC, 68, 3585. O O O O

R 1~

'l~r

'Pr

",R z

24-98% ee = 42-87%

42


I.A.8-7 Cowden, C.J., OL, 5, 4497. Cl

R"

H

.. CO2H R1

+ ~N

N

Cl $208"2Ag+~

H

[~N

N

R"3~~ Cl

R1 Cl 27-88%

I.A.8-8 Davies, H.M.L. et al., JACS, 125, 6462; Sengupta, S. et al., A G(E), 42, 6405. BOC .CO2Me Boc CO2Me R~~) + N2~Ar Rh2(S'DOSP)4~ s n R L__~)n 58-94% ee = 77-94% de = 76-94% I.A.8-9 Lu, X. et al., AG(E), 42, 1035; Kraus, G.A. et al., TL, 44, 659. ~O n O -~ ~ PPh3 EtO2C + NPh ~ EtO2C NPh

X

O

H i~) 74-88%

I.A.8-10 Shanmugan, P.; Miyashita, M., OL, 5, 3265; Yadav, J.S. et al., TL, 44, 6501. OSiRa3 Raasi'OTf ~ R @ ~ R1 R" ''~?" "" R1 .[. AIR23 CH2C12'"50~ R2

90-95% anti from trans-epoxide syn from cis-epoxide I.A.8-11 Urabe, H.; Sato, F. et al., JACS, 125, 4036; Makino, T.; Itoh, K., TL, 44, 6335.

(

R iprMgCI, Ti(Oipr)4 ~ .78-,00C OCOR1

.R1 OH 62-76%


43

I.A.8-12 Lee, H.-Y.; Kim, Y., JACS, 125, 10156.

~ R

2N " N~ph R1

-_R1R " 2 Ph-Me, ll0~

R

35-68%

"OH

I.B. Carbon-Carbon Double Bonds

(see also: I.E. 1) I.B.1. Wittig-Type Olefination Reactions

I.B.I.1 Ley, S.V. et al., TL, 44, 7779; Taylor, R.J.K. et al., CC, 2284. R A O H 1. TPAP, NMO, CH2C!2,4A M S R ~ R1 2. PhaP+CH2R1X', BaLi, THF (one pot)

13-94%

I.B.1-2 Moorhoff, C.M., M, 134, 429; Kulkarni, M.G. et al., TL, 44, 4913; Katsumura, S. et al., T, 59, 4945; Hoffmann, H.M.R. et al., S, 1844.

R1-CHO-I-

Ph3I~~~ O

R

LDA

~

O

R O O 29-70% Z:E = 1-5:1

I.B.1-3 Taylor, R.J.K. et al., TL, 44, 7735; Sano, S.; Takemoto, Y.; Nagao, Y., TL, 44, 8853. O CO2Me KHMDS ~ fCO2Me Bu3Sn/-~--NCHO + (CF3CH20)2P--"/ THF,-780C ~Ba3Sff "--" 82% 16-Cr-6 E:Z = 3.3:1 I.B.1-4 Reichwein, J.F.; Pagenkopf, B.L., JOC, 68, 1459; Augustyns, K. et al., TL, 44, 6231; see also: Cacatian, S.T.; Fuch, P.L., T, 59, 7177. O R 34 1. BaLi, THF,-78"C O~'OR4 O~~ I~,,,OR i~'OR3

1. saponify

R"

2.

1 R" 2 R

R2 61%

44


I.B.1-5 Taylor, R.J.K. et al., TL, 44, 7209. O

O

t uo 18 r6 Ph-Me, 700C (EtO)2P~O

14-25%

I.B.1-6 Pihko, P.M.; Salo, T.M., TL, 44, 4361. R

%

NaI MeO2CII (OT~ + R-CHO THF,-780C~ Nail,

/~/ MeO2C 88-99% Z:E = 2.33-13.3:1

I.B.1-7 Reuter, D.C. et al., S, 2321. U~PPh2 1. Nail, DMF S" -I- R-CHO BocHNO 2. DMSO, A or TFA, CH2CI2

H2NO2S/~-~R 26-79%

I.B.1-8 Albrecht, B.K.; Williams, R.M., OL, 5, 197; Berthelette, C. et al., OL, 5, 4851; Lequeux, T.; Pazenok, S. et al., TL, 44, 8127; Kittaka, A. et al., JOC, 68, 7407.

o

c

O + I

~/N~ LHMDS,DMPU ,,, H DMF. 0oc Cbz L-.SO2Bt

O I

79% E:Z =5:1 I.B.1-9 Taylor, R.J.K. et al., OL, 5, 4441 and AG(E), 42, 1387; Pasetto, P.; Franck, R.W., JOC, 68, 8042. M I ~ I~

M ~eBon2 O2

KOH, CC14 tBuOH/H20' 80~

Me OBn 50%

E:Z = 1:8


45

I.B.I-10 Nenajdenko, V.G. et al., OBC, 1, 1906. Br R1

Br

2. CBr4, CuCI 43-97%

I.B.I-ll Murai, T. et al., JOC, 68, 7979. Se Se . ~,~,~.CHO ~.~ BuLi ~ ~ ~ n , ArL N"On + NR2 THF,0~ A NR 2 TMS 44-99% I.B.I-12 Aggarwal, V.K. et al., JACS, 125, 6034. H 1. tBuOK, Ph-Me, 0~ R,,"~ N,,N~Ts 2. R1-CHO, CIFeTPP, PTC, P(OMe)3

R ~

R1

79-95% E:Z = 5.25-49:1 CIFeTPP = meso-tetraphenylporphryn iron chloride

I.B.2. E l i m i n a t i o n s

I.B.2.a. E l i m i n a t i o n s of A l c o h o l s and Derivatives

l.B.2.a-1 Sai, H. et al., S, 201; Bull, S.D. et al., CC, 2184; Bettadaiah, B.K.; Srinivas, P., SC, 33, 3615; Kraus, G.A.; Cui, W., SL, 95; Whitehead, R.C. et al., T, 59, 4827; Firouzabadi, H.; Iranpoor, N. et al., SC, 33, 3653; Maier, M.E. et al., S, 1324; Aramini, A.; Allegretti, M. et al., JOC, 68, 7911. HOk /CO2Me EDC,CuCl2 R~__/CO2Me H' "'~---~'"H R1 NHR

...... ~

Ph-Me,80~

threo

\

NHR 48-99% (E)

I.B.2.a-2 Nishiyama, K. et al., TL, 44, 4027; Kotera, M. et al., SC, 33, 3727. TBDMSO~B (TMS)aSiH,ph.H, . . . . 80~ _TBDMSO-~o~B PhH~O S

~ 1 NHPh S

49.82%

46


l.B.2.a-3 Mangaleswaran, S.; Argade, N.P., S, 343. O ArN~ O

1. R-CHO, TPP,_THF, reflux _~ H O 2 C , ~ - R 2. HCI, AcOH, reflux HO2C" 82-88%

l.B.2.b. Eliminations of Halides

I.B.2.b-1 Ichikawa, J. et al., JOC, 68, 7800. F3C~ Nuc-M _~ F2C~Nuc SiMe2Ph THF,-78~

SiMe2Ph 51-99%

I.B.2.c. Other Eliminations

I.B.2.c-1 Mioskowski, C.; Falck, J.R. et al., JACS, 125, 3218; Kim, Y. et al., JOC, 68, 180; Ranu, B.C. et al., S, 1012. CrCI2 CO2R1 R.CHO + X3CCO2R1 -~" R ' ~ THF, rt X 91-99%

I.B.2.c-2 Concellon, J.M.; Bardales, E., JOC, 68, 9492. O O SmI2 Ar Ar NR2 "~ R1 MeOH NR 2 67-95% Z selectivity = 98% I.B.2.c-3 Zard, S.Z. et al., OL, 5, 2907. EtO~'~S R~R

1 lauroylperoxide NO2

DCE, reflux

R ~

R1

53-82%


47

I.B.2.c-4 Malhotra, S.V., TA, 14, 645. BuLi, ipr2NH, chiral amines o THF 50-82%

ee = 39-95% I.B.2.c-5 Sinay, P. et al., EJOC, 2678. SePh OOe t, uOO.,i Oi r>4 B n O , . . y . ~ , OBn BnO

~

BOnn~.~~,, OBn BnO 60%

I.B.2.c-6 Zhang, Y. et al., TL, 44, 9349. OR~

OH

Sml2 ._ R~J%CCI2 CC13 THF,rt 70-96% v

I.B.3. Olefin M e t a t h e s i s

I.B.3-1 Grubbs, R.H. et al., JACS, 125, 10103, 11360. "Synthesis, Structure, and Activity of Enhanced Initiators for Olefin Metathesis." I.B.3-2 Blechert, S. et al., T, 59, 6545; Choi, T.-L.; Grubbs, R.H., AG(E), 42, 1743; Buchmeiser, M.R. et al., CC, 2742; Grela, K.; Kim, M., EJOC, 963; Lamaty, F. et al., OM, 22, 2426; Fogg, D.E. et al., OM, 22, 3634; Basset, J.-M. et al., CEJ, 9, 971; Taber, D.F.; Frankowski, K.J., JOC, 68, 6047. "Ruthenium Olefin Metathesis Catalysts with Modified Styrene Ethers: Influence of Steric and Electronic Effects." I.B.3-3 Cho, J.H.; Kim, B.M., OL, 5, 531. "An Efficient Method for Removal of Ruthenium Byproducts from Olefin Metathesis Reactions." I.B.3-4 Lavastre, O.; Kappe, C.O. et al., JOC, 68, 9136. "Microwave-Assisted Ring-Closing Metathesis Revisited. On the Question of the Nonthermal Microwave Effect."

48


I.B.3-5 Neipp, C.E.; Martin, S.F., JOC, 68, 8867; Yang, Y.-K.; Tae, J., SL, 1043; Murphy, J.A. et al., OL, 5, 2785; Ibrahim, Y.A. et al., T, 59, 7273; de Fays, L.; Ghosez, L. et al., TL, 44, 7197; Beaulieu, P.; Ogilvie, W.W., TL, 44, 8883; Thanh, G.V.; Loupy, A., TL, 44, 9091; Florent, J.C. et al., TL, 44, 2579; Krafft, M.E. et al., TL, 44, 839; Lovely, C.J. et al., TL, 44, 1379; Gennari, C. et al., TL, 44, 7913 and T, 59, 8803; Manzoni, L.; Scolastico, C. et al., S, 2363; Nantermet, P.G.; Selnick, H.G., TL, 44, 2401; Vederas, J.C. et al., OL, 5, 47; Kaliappan, K.P.; Kumar, N., TL, 44, 379; Karama, U.; Hofle, G., EJOC, 1042; Chaikof, E.L. et al., TL, 44, 89; Landais, Y. et al., JOC, 68, 2779; Mol, J.C. et al., OM, 22, 5291; Werner, H. et al., OM, 22, 1558; Bohmer, V. et al., CEJ, 9, 3375; Dutton, C.J. et al., BMCL, 13, 321; Srikrishna, A. et al., TL, 44, 7817; Fischer, H. et al., TL, 44, 7121; Chao, W.; Weinreb, S.M., OL, 5, 2505; Miller, S.J. et al., JOC, 68, 2728; Iqbal, J. et al., JOC, 68, 5006; Postema, M.H.D. et al., JOC, 68, 4748; Chen, X.; Wiemer, D.F., JOC, 68, 6597; Danishefsky, S.J. et al., AG(E), 42, 1280; Evans, P.A. et al., AG(E), 42, 1734; Snieckus, V. et al., OL, 5, 3519; Zhu, L.; Mootoo, D.R., OL, 5, 3475; van Koten, G. et al., AG(E), 42, 228; Gurjar, M.K. et al., OBC, 1, 1366. O O N~R

PhCH=Ru(PCy3)CI2X~

~[~'n

N~R ~ } n

CH2C!2, rt

75-97% JACS, 125, 9582; Yang, Y.-K.; Tae, J., SL, 2017; Lievre, C. et al., EJOC, 2336.

I. B .3 - 6 Hansen, E.C.; Lee, D.,

MeO

O X\ , p , ~ ~ R

o.L x

CH2Ci2,reflux ~

Ze,~l-_ (~~Y _ ~ MeO

~

~ ~ MesN~INMes

n

PhCH"l~h"Cl I -CI PCy3

MeO \\ Me MeO

~'P

n

35-92%

I.B.3-7 Lee, H.-Y. et al., OL, 5, 3439; see also" White, B.H.; Snapper, M.L., JACS, 125, 14901. X \

+

~'R

CH2CI2 MesN.

NMes

HYCI PhC "I~CI PCy3

63-93%


49

I.B.3-8 Sibi, M.P., OL, 5, 2883; Clark, J.S. et al., OL, 5, 89; Grigg, R. et al., TL, 44, 4899; Kim, D. et al., TL, 44, 7043; Martin, S.F. et al., OL, 5, 3523; Nemoto, H. et al., OL, 5, 2939; Nishida, A. et al., SL, 1207; Brown, R.C.D. et al., OL, 5, 3403; Fogg, D.E. et al., OM, 22, 1986. "~ O R1 R2 CH2Cl2,~reflux ~- C ~ ~

kJ

MesI~NMes P hCH::I~h"CI I "CI

PCy3

II-

19-88%

I.B.3-9 Lee, H.-Y.; Kim, B.G.; Snapper, M.L., OL, 5, 1855; Kulkarni, A.A.; Diver, S.T., OL, 5, 3463; Diver, S.T. et al., OL, 5, 3819. ~ R

MesN_ NMes

Phem

i -CI PCY3

II1 44-89% E:Z = 1.3-100:1

I.B.3-10 Morill, C.; Grubbs, R.H., JOC, 68, 6031; see also: Bisaro, F.; Gouverneur, V., TL, 44, 7133.

efB~ ~

+

M

I

RI

I

CH2C12,reflux M~sS,~NMes PhCIt:IRIk"cCII

R~B~~ 31-99% E:Z = 7-20:1

PCY3

I.B.3-11 Lazarova, T. et al., OL, 5, 443. X .a'

~

, ,Me

f'

F

Me~"~'~CHO CH2CI2,40~

'o"

M d'''~ O" ~ ' ~ ~'OR1

MesNN~,NMes p hCH: l{h"CI I "CI PCY3

,Me

''CHO f-'OR

O~'~,OR 1 42-78%

50

ORGANIC SYNTHESISn2004

I.B.3-12 Rivard, M.; Blechert, S., EJOC, 2225; Compain, P.; Martin, O.R. et al., OL, 5, 3269; Chang, S. et al., OL, 5, 3041; Pietrusiewicz, K.M.; Grela, K. et al., OL, 5, 3217. CuCl, CH2Ci2~400C R,,~~CN 1~~ + ~'~CN MesN_yNMes 27-74% PhCH:1~CI (10"52% W/outCu)

~y~

I.B.4. Other Carbon-Carbon Double Bond Formin~ Reactions

I.B.4-1 Zhang, X.P. et al., OL, 5, 2493 and JOC, 68, 3714, 5925 and OM, 5, 4905; Wang, J. et al., OL, 5, 2243; Woo, L.K. et al., OM, 22, 1468; Trauner, D. et al., OL, 5, 4113; Mete, A. et al., TL, 44, 6621; Taber, D.F.; Storck, P.H., JOC, 68, 7768. Fe(TPP)CI' PPh3 ~. R ~ C O 2 R 2 ~ R 10 + N2~'CO2R2 Ph-CO2H,Ph-Me, 80~ R1 42-93%

E:Z = 2.7-6.38:1 I.B.4-2 Takeda, T. et al., TL, 44, 7897. 0 + Cp2Ti[P(OEt)3]2 CI~OR 2

R1 49-85%

I.B.4-3 Kreher, U.P.; Strauss, C.R. et al., OL, 5, 3107; Trenkle, W.C. et al., OL, 5, 3333; Sevenard, D.V., TL, 44, 7119; Cardillo, G. et al., SC, 33, 1587; Ballini, R. et al., TL, 44, 9033; Kiyooka, S. et al., TL, 44, 927. O O ~CHO ~R2 DIMCARB,~ ~ R 2

I.B.4-4 Zhdankin, V.V. et al., JOC, 68, 1018. Ph-CHO +

TsO" Ph3I~ "l+Ph

Nue ~ Nuc Ph 40%


51

I.B.4-5 Wicha, J. et al., OL, 5, 2789. Si3RI~O R2 N~N R + L s~N'N 02 Ph

R•R

LHMDS THF, -78~

2

78-84% E:Z = 1.63-2.12:1

I.B.4-6 Mukai, C. et al., TL, 44, 1583.

PhO

~

~ CO2R

tBuOK tBuOH, rt

CO2R

PhOtON,/

CO2R

72-98%

I.B.4-7 Ronsheim, M.D.; Zercher, C.K., JOC, 68, 4535. O O 1. Et2Zn, CH212,CH2CI2 O R,~J ~ 2.12 ~ L ~ .,R1 R1 3. aq Na2S203 R" " ~ y 4. DBU O (one pot) 59-86% I.B.4-8 Jung, M.E.; Wasserman, J.I., TL, 44, 7273. Me Me Ac WCI6 Me I /OAc CH2C12,450C~ C1 ~ ~ ~ 7 .... H

H

94%

I.B.4-9 Hon, Y.-S. et al., T, 59, 1509. rrlv O O 1~ CH2Br2,Et2NH Ar R ~ CH2C12or MeCN Ar

R

0-85%

I.B.4-10 Urabe, H.; Sato, F. et al., OL, 5, 67. R

TSXNBn /

TS~NBn

I!§ II 1

Ti(Oipr)4,iprMgCI ~Et20, -50~

R'~

(also with BZ in place of Ts)

R1 56-93%

52

ORGANICSYNTHESISm2004

I.B.4-11 Etzkorn, F.A. et al., JOC, 68, 2343. "Serine-cis-proline and Serine-trans-proline Isosteres: Stereoselective Synthesis of (Z)- and (E)-Alkene Mimics by StillWittig and Ireland-Claisen Rearrangements." I.B.4-12 Wong, K.-T.; Hung, Y.-Y., TL, 44, 8033. R ~ O + [~>---MgBr I'0~ R1 2. AcCI, 50~ R~

40-90%

I.B.4-13 Yoshida, K.; Hayashi, T., JACS, 125, 2872. PhO2S',~~ph

4- ArTi(Oipr)3

kr

[Rh(OH)(BINAP)]2~. THF, 40~

Ph 97-99%

I.B.4-14 Liu, R.-S. et al., JACS, 125, 9294. OH TpRu(PPha)(MeCN)2PF6,LiOTf v

Ph-Me, ll0~

52-91%

I.B.4-15 Luh, T.-Y. et al., OL, 5, 4489. IL

R1 + R2MgX

Ni(acac)2, va33 ~

~

R2 R

1

48-73% I.B.4-16 Komatsu, M. et al., JOC, 68, 6164. R3Me2Si~1

O

R" ~ ~ R 2 Ph-H, 180~

R1 R~OSiMe2R3 R2 44-93% Z:E = 3-24.5:1

I.B.4-17 Dhal, R. et al., S, 2269. Me Me"~OMe13(" +

N~ H O R._~-/_. k1k2

TMS-OTf,CSA, TEA CH2C12,55~

~

LN~

O R_.~~.. k1k2

73-90% ee = 99 %


53

I.B.4-18 Murakami, M. et al., JACS, 125, 4720. R

R

CN~~ Ph

TMS +

CpRu(PPh3)2CI NaPF6, 150~ 66-76%

I.B.4-19 Fallis, A.G. et al., OL, 5, 2989. R

OH

R1

1. R1MgX, THF/Ph-Me, reflux

R

2. R2-X, Pd(PPh3)4, reflux

R2~-~_OH 10-73%

\

I.B.4-20 Dixneuf, P.H. Eisenstein, O. et al., JACS, 125, 11964. R

R

+ HO~C.R 1

dioxane, r t

.....

1

30-98%

I.B.4-21 Curini, M. Epifano, F. et al., SL, 552. Ph

R 1 + R-CHO

O

Yb(OTf)3 y

90~

Ph

R R1 50-84%

I.B.5. Vinylations

I.B.5-1 Ishii, Y. et al., JACS, 125, 1476; Kita, Y. et al., OL, 5, 3703; Roglans, A. et al., OL, 5, 1559; Xu, J.-H. et al., SC, 33, 773; Kondolff, I.; Doucet, H.; Santelli, M., TL, 44, 8487; Doucet, H.; Santelli, M. et al., SL, 841; Whiting, A. et al., TL, 44, 7645; de Meijere, A. et al., EJOC, 2375; Tobe, Y. et al., OL, 5, 341 l; Hou, X.-L.; Dai, L.-X. et al., OL, 5, 3651; Jacobs, P.A. et al.,AG(E), 42, 3512; Oh, C.H.; Lim, Y.M., TL, 44, 267; Iqbal, J. et al., TL, 44, 353; see also: Tanaka, T. et al., JOC, 68, 5550; Yao, C.-F. et al., JOC, 68, 4030. Ar-H +

~,,,,CO2R

Pd(OAc)2, 02, H7PMo8V4040 AcOH, 90~

Ar~CO2 62-75%

R

54


I.B.5-2 Miura, M. et al., AG(E), 42, 4672; Inoue, A.; Shinokubo, H.; Oshima, K., JACS, 125, 1484. Ar-COCI + ~ R [RhCI(C2H4)2]2~ A r ~ R Ph-Me2, reflux 51-98%

og:

I.B.5-3 Grigg, R. et al., TL, 44, 7969. Pd(OAc)2,In, TFP Ar-I + ~ \ + R1.CHO R additives

Ar

R1 R

0-88% I.B.5-4 Zeni, G. et al., SL, 579, 1880; Hou, Z. et al., JACS, 125, 1184; Uemura, A. et al., OL, 5, 2997; Braga, A.L. et al., JOM, 682, 35; Cai, M. et al., JOM, 681, 14, 98 R1 R1 R + B u T e ~ Y R 2 PdCI2,CuI, TEA ./~~yR2

MeOH

R~

71-88%

LB.5-5 Peyrat, J.-F. et al., TL, 44, 6703; Betzer, J.-F. et al., TL, 44, 7553; Knochel, P. et al., OL, 5, 1059. R-M + CI~ R 1 PdCl2(dppf) _ R~R 1 THF, 68"C 60-96% I.B.5-6 Menzel, K.; Fu, G.C., JACS, 125, 3718; Fu, G.C. et al., AG(E), 42, 5079; Duchene, A. et al., TL, 44, 1647 and S, 448; Mazur, A.W. et al., OL, 5, 1163; Moloney, M.G. et al., OBC, 1, 3726; Li, H. et al., SC, 33, 3761; Guanti, G.; Riva, R., OBC, 1. 3967. I L ~ B r + Bu3Sn.~ [(~-allyl)PdCll2'Mep(tBu)2~ H H t ~ " HH R1 ~ R1 55-96% (for 13-hydrogencontainingalkyl bromides) I.B.5-7 Franzen, J.; Backvall, J.-E., JACS, 125, 6056. M ~ 2 ~ CO2Me _ ~ ~ _ RCO2Me CO2Me (~/ L Pd(O2CCF3)2,BQ " ( THF, reflux tI x~

73-94%


55

I.B.5-8 Marson, C.M. et al., T, 59, 4377; Lando, V.R." Monteiro, A.L., OL, 5, 2891; Sato, F. et al., OL, 5, 523. O O

~

B(OH)2 + r ~ R 1

R" ~

B

)n

Pd(PPh3)4,aq Na2CO3 EtOH/Ph-Me, reflux

R 92-98%

I.B.5-9 Zhang, X." Larock, R.C., OL, 5, 2993, 1579; see also: Bhat, N.G. et al., TL, 44, 7175. R

+ R ~

R + Ar-B(OH)2 PdCI~KF ~ H20/DMF, 100~ R1

R1

56-93%

I.B.5-10 Luo, F.-T. et al., TL, 44, 7249. O

1. Me2S.BHCy2, THF 0*C~ rt

R

R~~NMe2 47-73%

2. BrCI-I2CONMe2,Pd(dba)2 PCy3, K3PO4~THF, 70"C

I.B.5-11 Buchwald, S.L. et al., OL, 5, 3667. O

O

MeHNCH2CH2NHMe

R,,'~ NH ~1

4-

~"X

K2CO3or Cs2CO 3 (62-95%)

I.B.6. Ailene Forming Reactions

I.B.6-1 Huang, X.; Xiong, Z.-C., TL, 44, 5913 and CC, 1714. O R

PPh2 4- R1S-Li + R2-CHO

R

THF, rt

~

R2

RIs/ 61-87%

56


I.B.6-2 Sato, F. et al., OL, 5, 2145; see also: Hsung, R.P. et al., OL, 5, 2663. _OMe _OMe N~ Ph -I- R ( Ti(Oipr)4,iprMgCI H Ph Ar~J 1_ X Et20,-35~ AP'" R1 -

R

45-74% dr = 13.3-49:1 I.B.6-3 van Vranken, D.L. et al., JOC, 68, 4955. Uoc

RS~ ~

dppe, FeCI2 R1 + BocN3 DCE, 0~

RS--~ = R1

31-73% I.B.6-4 Furstner. A.; Mendez, M., AG(E), 42, 5355. R

/ ~ ~

RIMgBr,Fe(acac)3 Et20 or Ph-Me,-5~

R1 'OH 54-98% syn:anti = 1.2-49:1

I.B.6-5 Leclerc, E.; Tius, M.A., OL, 5, 1171. MeO~O TMS H BuLi .~ Me 6 +Ph ~r__~O--" tBu Md~' LN--'X ~2 THF' "78-~"400C

O

74% tBu I.B.6-6 Evans, C.A.; Miller, S.J., JACS, 125, 12394. O O R~RI + ~CO2Et ~ ' ~ R ~

CO2Et

50-98%


57

I.B.6-7 Sato, T. et al., CPB, 51,966. 1. tBuMgCi ~~)( ~_~CI 2. EtMgCi, THF, .78oc 6IS--Tol 3. PhSO2C(Li)RR1 THF, THF, -78~ ~ rt

0-65 %

I.C. Carbon-Carbon Triple Bonds I.C-I Leadbeater, N.E. et al., OL, 5, 3919.

R~~ff.._X +

R1 ~tW,NaOH~

R~~..._

R1

~

PEG/H20 10-99%

I.C-2 Gelman, D.; Buchwald, S.L., AG(E), 42, 5993; Leadbeater, N.E.; Tominack, B.J., TL, 44, 8653; Soheili, A. et al., OL, 5, 4191; Andrus, M.B. et al., OL, 5, 3317; Heuze, K. et al., CC, 2274; Doucet, H.; Santelli, M. et al., OBC, 1, 2235; see also: Mori, Y.; Seki, M., JOC, 68, 1571; Spivey, A.C. et al., JOC, 68, 1843; Nolan, J.M.; Gmins, D.L., JOC, 68, 3736; Walker, I.V.; Rokita, S.E., JOC, 68, 1563; Vargas-Berenguel, A. et al., OL, 5, 2389; Chanteau, S.H.; Tour, J.M., JOC, 68, 8750; Erdelyi, M.; Gogoll, A., JOC, 68, 6431; Utesch, N.F.; Diederich, F., OBC, 1,237. R~/~C!

+ ~R

1 PdCI2(MeCN)2,Cs2CO3 MeCN, 70-95~ ipr P.CY2

R~//-~___ 77"95%

i p r ~ ipr I.C-3 Zou, G. et al., TL, 44, 8709. R

--

-I- R1-B(OH)2

PdCl2(dppf),Ag20,K2CO3

R

- -

R 1

0-90%

I.C-4 Shirakawa, E.; Hiyama, T. et al., JOM, 670, 132. [PdClffl3-CaHs)]2 R ~ SnBu3 ~ R ~

~ p p N~Ph~.OA c

~ R 84-93%

R1

58


I.C-5 Plenio, H. et al., AG(E), 42, 1056 andOM, 22, 4098; Kollhofer, A.; Plenio, H., CEJ, 9, 1416; Hillerich, J.; Plenio, H., CC, 3024; Beletskaya, I.P. et al., TL, 44, 5011; Gallagher, W.P.; Maleczka, Jr., R.E., SL, 537 and JOC, 68, 6775; Eckhardt, M.; Fu, G.C., JACS, 125, 13642; Ravina, E. et al., T, 59, 2477; Fairlamb, I.J.S. et al., S, 2564; see also: Brimble, M.A. et al., OL, 5, 4425; Prasad, K. et al., OPRD, 7, 733; Kotschy, A. et al., JOC, 68, 3327; Novak, Z.; Kotschy, A., OL, 5, 3495; Ho, T.-I. et al., CC, 2146; Muller, T.J.J. et al., JOC, 68, 1503. 1~~/C.+

__

RI Na2PdCI, Cu,, (1-ad)2PBn.HBr R , ~ / : ~ DMSO, 100~

~

....R1

~ - ' -

62-96% I.C-6 Low, P.J. et al., JOM, 670, 178; Braga, A.L. et al., TL, 44, 1779; Zeni, G.; Braga, A.L. et al., TL, 44, 685; Forsyth, C.J. et al., BMCL, 13, 2127. R

CI,~CI R~

Pd(PPh3)4,CuI, ipr2NH

+

R

~

]

/

-

CI~

"CI

Rj ~

~'~R 30-60%

I.C-7 Negishi, E. et al., OL, 5, 1825. X X + XZn - -

TMS

PdCI2(DPEphOS)THF~ 65-99%

TMS

I.C-80tera, J. et al., T, 59, 5635. F F

tBuOK

Ph---~

~=/ SO2Ph

"~ Ph "-'O--P(OEt)2 TI-IF O

O

R 92%

I.C-9 Shinokubo, H.; Oshima, K. et al.,AG(E), 42, 5613. N,.OMe TsO,,~ N,,OMe LDA R ~ R1 40-74%

ct


59

I.C-10 Dunetz, J.R.; Danheiser, R.L., OL, 5, 4011. 17,,,NH + I EWG

Bt ~

R1 KHMDS,CuI pyr, rt

/N --- R1 EWG 42-78%

I.C-II Miljanic, O.S.; Vollhardt, K.P.C.; Whitener, G., SL, 29; Gleiter, R. et al., S, 2535; Konig, B. et al., JOC, 68, 9379; Cummins, C.C. et al., OM, 22, 3351; Lipton, M.A. et al., JOC, 68, 8471; Young, D.G.J. et al., JOC, 68, 3494; Tykwinski, R.R. et al., CEJ, 9, 2542. R R

~

~

(Me3CO)W-CCMe3~ Ph-Me, 80~

~/~

27-54% R R

I.C-12 Poloukhtine, A.; Popik, V.V., JOC, 68, 7833. o hv ~.- R "'-"~ R1 R

R1

MeOH

50-90%

I.C-13 Kurita, J. et al., TL, 44, 8589. Me I

~b

+ R-COCI

PdCI2(PPh3)2 DCE

Ar R 63-86%

Ar I.C-14 Cheng, C.-H. et al., OL, 5, 881.

- - . - - - .

~ +N ~ [

Bu3Sn"

+ R I ~ CI

CN

Pd(PPh3)4 ~ R 2 Ph-Me, rt, 8h

i~3

74-80%

60


I.C-15 Abele, E. et al., TL, 44, 3911.

Ar-Br + CI~ B r

Pd(OAc)2,dppb,KOH 18-Cr-6,Ph-Me

Ar

Ar 29-61%

I.C-16 Shun, A.L.K.S.; Tykwinski, R.R. JOC, 68, 6810; Tykwinski, R.R. et al., JOC, 68, 1339. "Synthesis of Naturally Occurring Acetyenes v/a an Alkylidene Carbenoid Rearrangement."

I.D. Cyclopropanations

I.D.1. Carbene or Carbenoid Additions to a Multiple Bond

I.D.I-1 Katsuki, T. et al., TA, 14, 823; Sugimura, T. et al., TA, 14, 881; Perez-Prieto, J.; Stiriba, S.-E.; Moreno, E.; Lahuerta, P., TA, 14, 787; Nakada, M. et al., JACS, 125, 2860; Kwong, H.-L.; Che, C.-M. et al., TA, 14, 837.

N2

O Co(II)-salen~ R1 10-93% ee = 3 8 - 9 8 %

I.D.1-2 Aggarwal, V.K. et al., OL, 5, 4417.

Ph~OH

R2

Me'~~ I N ' R 1 Me R

Zn(CH2I)2

Phi_ IOH

R2

CH2C12,0~ ~ Met" I ~ ~ R 1 Me R 93-96% dr = 8-49:1

I.D.1-3 Wurz, R.P.; Charette, A.B., OL, 5, 2327; Muller, P.; Ghanem, A., SL, 1830; Muller, P. et al., TA, 14, 779. R

R~ + NO2~n IR1 O

PhI(OAC)2neat rt ~,

~NO2 "O~r'-R1 75-91%


61

I.D.1-4 Zhang, X.P. et al., JOC, 68, 8179; Salvadori, P. et al., CC, 2466; Reiser, O. et al., TA, 14, 765; Muthusamy, S. et al., SL, 1599; see also:, Charette, A.B.; Janes, M.K.; Lebel, H., TA, 14, 867; Iwasa, S.; Nishiyama, H. et al., TA, 14, 855; France, M.B. et al., TL, 44, 9287; Che, C.-M. et al., TL, 44, 8733; Edulji, S.K; Nguyen, S.T., OM, 22, 3374; Moore, J.D.; Hanson, P.R., TA, 14, 873; Berkessel, A. et al., CEJ, 9, 4746; Mezzetti, A. et al., TA, 14, 845; Mizuno, K. et al., JOC, 68, 7700; Mayoral, J.A. et al., TA, 14, 773. R1 R

+ N2CHCO2Et

Co(Ph4Porphyran) -~ Ph.Me, 80~

~,A R CO2Et 89-99% cis:trans = 1:2.3-3.3

I.D.1-5 Miki, K.; Ohe, K.; Uemura, S., JOC, 68, 8505; Donaldson, W.A. et al., JOC, 68, 901. R

OCOR2

[RuCI2(CO)~2

R ~

OCOR2

DCE, 50"C 24-97% cis:trans = 1-1.63:15.7-1

I.D.1-6 Dolbier, Jr., W.R. et al., OS, 80, 172; Xu, W.; Chen, Q.-Y., OBC, 1, 1151; Yang, Z.-Y., JOC, 68, 4410. ~"~co2tBu

F F %

NaF + FSO2CF2CO2TMS Ph-Me, reflux

CO2tBu 55%

I.D.1-7 Shi, Y. et al., JACS, 125, 13632. R1 R~ R 2

CH2I~ ZnEt2, CH2C12 n

o

.COzMe

R1 R,~ ee

'~r

R2

43-84% = 72-91%

I.D.1-8 Takai, K. et al., JACS, 125, 12990; Paugam, J.P. et al., SL, 485. CHI3, CrCI2, TEEDA R/'~

THF, 25~

~

R ~ I 37-97% trans:cis = 10-49:1

62


I.D.1-9 Motherwell, W.B. et al., CC, 2656. R1

EtQ~___

Zn(Hg), ZnCI2, TMS-CI Et20, reflux

R3 9-88% trans:cis = 1-19:1

I.D.2. Other Cyclopropanations

I.D.2-1 Gaunt, M.J. et al., AG(E), 42, 828; Florio, S. et al., JOC, 68, 1394; de Meijere, A. eta., S, 956; Ballini, R. et al., SL, 1704. O O ph~Cl + ~.~,,.EWG Na2CO3,MeCN, 800C ~ ~ . ~>% - Ph "' EWG 63-82% trans:cis = >19:1

I.D.2-2 Diez, D. et al., S, 53 and OL, 5, 3687. OR S02Ph LDA ._ THF, .78~

S02Ph

,,,....-

68-99%

I

I.D.2-3 Tang, T. et al., JACS, 125, 13030. i~ R21

~ BPh4" S3 + ~/~+Te~~"~R 1 ~....i.,. R 9e e

O LiTMP HMPA

R2,--

R1 R

1-99% 7.3-99:1 ee = 93-99% I.D.2-4 Szymoniak, J. et al., TL, 44, 4827; Bertus, P.; Szymoniak, J., SL, 265 and JOC, 68, 7133; Laroche, C.; Bertus, P.; Szymoniak, J., TL, 44, 2485; de Meijere, A. et al., OL, 5, 753. OR R1 R1R @ , ~ BuLi,ZrClzCI~ THF ~ R2~Me 50-85% trans:cis = 1-3.2:1


63

I.D.2-5 Taylor, R.E. et al., OL, 5, 1377. OH Tf20 R

~

OTES

pyr-Me2, -78~

~

R~ I C H O 84-89% trans:cis = 2.1-6:1

I.D.2-60uhamou, N.; Six, Y., OBC, 1, 3007. Ti(Oipr)*THFC'C5H9MgCI"~ ~

~

93% I.D.2-7 Cha, J.K. et al., OS, 80, 111. ~,,~Ph

CITi(Oipr)3' c'CsH9MgCI + MeCO2Et THF ~

H(~,Me " ~",/Ph " 80%

I.D.2-8 Dixneuf, P.H. et al., AG(E), 42, 5474; Ohno, H.; Tanaka, T. et al., OL, 5, 4763. / m RuCICp*(cod) R~ r X R1 X\ / R + N2CHCO2Et dioxane, 100oc CO2Et 60-75% I.D.2-9 Miki, K.; Ohe, K.; Uemura, S., TL, 44, 2019. OAc R2 R~R"1l ' O~ A c

~"~R 2

[RuCI2(CO)3]2 ~ Ph-Me, 60~ 18h 1-91%

I.D.2-10 Concellon, J.M. et al., JOC, 68, 1132. OH O

R~R3 R Cl

1. SmI2, THF, -25~ NR2 2. Sm, CH2I~ -30~

O

R

NR2

80-96%

64


I.D.2-11 Wessig, P.; Muhling, O., HCA, 86, 865. ~ ~NR hn, TsOH O\ , I-I"-.~~NR Ph" " ~ v OTs

NMI. CH2CI2~ phY"H~ 69-78%

I.E. T h e r m a l and P h o t o c h e m i c a l Reactions

I.E.1. Cycloadditions I.E.I-1 Brand, S. et al., OL, 5, 2343; Ito, H.; Iguchi, K. et al., TL, 44, 1259; Scheeren, H.W. et al., EJOC, 894; Uneyama, K. et al., CC, 2902. OR 1

Me t,~R1

TEA

OCl

+ II

Me I / v

Et ou R 45-75%

R

I.E.1-2 Mislin, G.L.; Miesch, M., JOC, 68, 433.

F E

71-82% I.E.1-3 Suzuki, K. et al., OL, 5, 3551; Durst, T. et al., CJC, 81,997. ~.OTf+EIO~ }n

OTBDMS

I

BuLi

THF, -78~ ~

I.E.1-4 Komatsu, M. et al., S, 1398. O TMS

'n~ OTBDMS I OEt I 43-75%

EK

Ph-Me, 180oc E

59-89%

/E


65

I.E.1-5 Padwa, A. et al., JOC, 68, 6238.

~

SO2Ph

SO2Ph

TEA ~ , ~ ~ ~H RI Ph-H, 800C R2 82-92%

I.E.1-6 Bashiardes, G. et al., OL, 5, 4915. Me,,N~CO2Me CI~CHO

Mf"N~

~',,,~'~~

R1

Ph-Me,reflux C

l

~

R1

CO2Me or l.tW

R

70-98%

I.E.1-7 Ishikawa, T.; Saito, S. et al., OL, 5, 3875, 3879. MeH OD~~,~NO2 "~ TEA,DMAP ~ Me"si'L'XO~ I ~O MeCN,0~ -~ rt ~R-~-N R O~iMe 2 75-95% /~ dr = 5-99:1 "~

+CIMe2Si

I.E.1-8 Rigby, J.H.; Wang, Z., OL, 5, 263. O X Ph-H, reflux

O X 55-88%

I.E.1-9 Jao, E. et al., TL, 44, 5033.

r +

Ph-Me, reflux .|'

Ph"

.

PIf

80%

66


I.E.I-10 Evans, D.A.; Wu, J., JACS, 124, 10162; Sprott, K.T.; Corey, E.J., OL, 5, 2465. CO2Me O Me f ~ ;"" II II + `% THF/Ph-Me,-78~ .~ i"~':" "\"" R1 ~ R1 O

R

R31,. _

R2

"ffO'l'OTf

OTf

II

R3

o

I

O

H-

R

84-99%

~._

Rz

ee = 9 1 - 9 9 %

I.E.I-ll Shindo, M. et al., S, 1441; Kouklovsky, C.; Langlois, Y. et al., S, 1419; Yamada, T. et al., S, 1462; Tadano, K. et al., SL, 1865. O

9

OLi

i

II

R~N,~

..~--N~B +

n

_

R

n

;o 48-93%

13-H:cx-H= 5.25-19:1 I.E.I-12 Krische, M.J. et al., JACS, 125, 3682; see also: Takacs, J.M.; Lesnov, A.P., OL, 5, 4317. O R1 O

EtOAc, ll0~ 71-86% de = 19:1 I.E.I-13 Sibi, M.P. et al., JACS, 125, 9306. O+R~~ Zn(OTf)%CH2C12,rt

O

RI . ~ H ~ O , ~ . ~ M e Ph

O 82-94% endo:exo = 1.3-17 ee (endo) - 89-96%


67

I.E.l-14 Pinho e Melo, T.M.v.D. et al., TL, 44, 6313.

CO2R 0*C~rt

O2R

N3

38-49% I.E.I-15 Ellman, J.A. et al., JOC, 68, 3; Armstrong, A. et al., TL, 44, 3915; Khrimian, A. et al., T, 59, 5475; Keay, B.A. et al., TA, 14, 749; Marchand-Brynaert, J. et al., JOC, 68, 9809; Hawkins, J.M. et al., OL, 5, 4293; see also: Paquette, L.A. et al., OL, 5, 2639; Klimova, E.I. et al., OBC, 1, 1210; Ruzziconi, R. et al., JOC, 68, 736; Timen, A.S.; Somfai, P., JOC, 68, 9958; Fringuelli, F.; Pizzo, F. et al., JOC, 68, 9263; Yang, Z.-Q.; Danishefsky, S.J., JACS, 125, 9602; Mohri, K. et al., CPB, 51, 502; Pedrosa, R.; Andres, C. et al., S, 1457; Dunach, E. et al., TL, 44, 8841; Thunberg, L.; Allenmark, S., TA, 14, 1317; Aly, A.A., OBC, 1, 756; He, Y.; Junk, C.P.; Lemal, D.M., OL, 5, 2135; Singh, V.; Kane, V.V. et al., OL, 5, 2199; Sarkar, T.K. et al., JOC, 68, 6919; Nakayama, J. et al., JACS, 125, 8255; Desimoni, G. et al., JOC, 68, 7862; Carreno, M.C. et al., CEJ, 9, 4118; Knappwost-Gieseke, C.; Winterfeldt, E. et al., CEJ, 9, 3849; Stoermer, M.J. et al., CEJ, 9, 2068; Barriault, L. et al., JOC, 68, 2317; Piettre, S.R. et al., JOC, 68, 7990; de la Pradilla, R.F. et al., CC, 2476; Livinghouse, T. et al., OBC, 1, 2038; Asao, N.; Yamamoto, Y. et al., JACS, 125, 10921. R
46-73%

I.G.2-15 Nozaki, K. et al., JACS, 125, 8555; Gusevskaya, E.V.; dos Santos, E.N. et al., JOM, 671, 150; Breit, B. et al., CEJ, 9, 425; Suades, J. et al., JOM, 669, 172. "Solvent-Free Asymmetric Hydroformylation Catalyzed by Highly Cross-Linked Polystyrene-Supported (R,S)-Binaphos-Rh(l) Complex."


91

I.G.3. Other Synthesis via Organometallics I.G.3-1 Ozaki, S. et al., JOC, 68, 4586; Liu, H.-J. et al., CC, 2490; Snider, B.B. et al., JOC, 68, 6451. O

~

~~,,.,CN

~

~,R1

O

De60oR'O .

------'~--n

ClO 4"

I.G.3-2 Hashimoto, S. et al., TA, 14, 817; Perez, P.J. et al., OM, 22, 4145.

CH2C12 It o

C02Me

~;~

O~-1-~

64-98%

X

I.G.3-3 Cai, M. et al., JCR(S), 485; Xie, M.; Huang, X., JCR(S), 584; Silveira, C.C.; Zeni, G. et al., JOC, 68, 662; Gevorgyan, V. et al., JOC, 68, 6251; Casey, C.P.; Dzwiniel, T.L., OM, 22, 5285. iBuMgBr, CP2TiCI2 R __/TMS I ' R1 R fTMS R

TMS Et20,

rt

~

-

\MgBr Pd(PPh3)4,THF

-

-

,\ R1

62-76% I.G.3-4 Kabalka, G.W. et al., JOC, 68, 7915; Miura, M. et al., JOC, 68, 6836; Larock, R.C. et al., JOC, 68, 339; Rayabarapu, D.K.; Cheng, C.H., CEJ, 9, 3164; Cheng, C.-H. et al., OL, 5, 3963 and JOC, 68, 6726; Xi, Z.; Takahashi, T. et al., JOC, 68, 1252. R4

R

R1 +

R4

oR'

3 CH2C12,rt

R1 R

65-90%

92


I.G.3-5 Molinaro, C.; Jamison, T.F., JACS, 125, 8076; Tsuchimoto, T.; Shirakawa, E. et al., CC, 2454.

R ~

R I + O~ ~

R2 Ni(eod,2,PBu3, Et3B

R,~,~~R

2

R~ OH 25-68% 19:1 I.G.3-6 Mascarenas, J.L. et al., JACS, 125, 9282. ~~> X \

R

Pd2(dba)3,p(Oipr)3 dioxane,100~

X ~ R 65-96%

I.G.3-7 Ajamian, A.; Gleason, J.L., OL, 5, 2409; Mori, M. et al., OM, 22, 30.

TBSO~ M~~ -M

TBS(~ TMS Co2(CO)&P(OMe)3,~ MI~

~

Ph-Me, reflux

M

TMS 93%

I.G.3-8 Zhu, G.; Zhang, Z., OL, 5, 3645; Krische, M.J. et al., JACS, 125, 7758; Widenhoefer, R.A. et al., OL, 5, 2699; Tanaka, K.; Fu, G.C., JACS, 125, 8078" Echavarren, A.M. et al., CEJ, 9, 2627. X~ ~ R / X

\

~

R

+ Ar-B(OH)2

Pd(PPh3)4,KF y . ~ A i Ph'Me'60~

~

r

21-90% I.G.3-9 Sato, F. et al., JOC, 68, 4980; Cha, J.K. et al., OL, 5, 2137; Tsukada, N. et al., JOC, 68, 5961; Yamamoto, Y. et al., CEJ, 9, 2469.

R1 Ts

+

RI - R --

>

....OTBS

iprMgCI' Ti(Oipr)4 ~ Et20, -780C

'"IOTBS R 63-88%


93

I.G.3-10 Knochel, P. et al., S, 1797 and CEJ, 9, 2789, 2797; Wu, J.; Yang, Z. et al., JOC, 68, 670; Fairlamb, I.J.S.; Taylor, R.J.K. et al., CC, 2194; Jackson, R.F.W. et al., OBC, 1, 140; Bailey, W.F. et al., JOC, 68, 1334; Li, S.; Dieter, R.K., JOC, 68, 969; Crotti, P. et al., OL, 5, 2173. Br,~Brh "!" P

1. RMgCI, Et20, -78--*0~

h~ E

CO2Et 2. E +

P

CO2Et 56-82%

I.G.3-11 Barluenga, J. et al., JOC, 68, 537 and CEJ, 9, 5725; Wulff, W.D. et al., JACS, 125, 8980; Katayama, H.; Nagao, M.; Ozawa, F., OM, 22, 586. RO M(CO)5 RO OMe R1 I ~ O M e ~ R1 -- I [ ~ ~ OH R2 R3]11~~4 R5 THF,reflux

R2 ~3

R4

R5

46-95%

I.G.3-12 Togo, H. et al., JOC, 68, 7629; Tsukade, N. et al., CC, 2404. O (.__ _

ZnorIn R

,._ (

H20/tAm-OH,A

CO2R 15-93%

I.G.3-13 Davies, H.M.L. et al., JOC, 68, 6126. Ar Rh2( DOSP)4 ~.~ A s ~,~q~j MeO2C,~N2 + T B S ~ tBuEt, 50~ - MeO2C .r ~--- R TBSO 33-98% de = 92-98 % ee = 62-92%

I.G.3-14 Oshima, K. et al., OL, 5, 3959; Reimelt, O.; Heck, J., OM, 22, 2097. ~,TMS TMS'CH2MgCI' C~ r R-Br + ~ ~ ~ ' R 1 Ph2P(CH2)6PPh2 R1 60-93%

94


I.G.3-15 Ishii, Y. et al., JOC, 68, 5974; Tanaka, T. et al., JOC, 68, 5909, 7722; Wang, K.K. et al., JOC, 68, 5832, 8545; see also: Chang, S. et al., OL, 5, 2687. R\1

R"~

-I-

,/~O

R1

\O Mn(OAc)2,Co(OAc)2, 0 2 .1~ R A ~ C O 2 RI~o

130~

H

8-91%

I.G.3-16 Knochel, P. et al., OL, 5, 2111; Rodriquez, D.; Selesto, J.P.; Sarandeses, L.A., JOC, 68, 2518. R1

R2Zn 4-

OCOC6F5

Bu

R1

CuCN.2LiCI ~ R~,,,,~, ~ THF, .10~ Bu 68-90% ee = 89-95 %

I.G.3-17 Isakov, V.E.; Kulinkovich, O.G., SL, 967; Lee, P.H. et al., JOC, 68, 7085; Sato, Y.; Oonishi, Y.; Mori, M., JOC, 68, 9858; Rajanbabu, T.V. et al., JAC, 68, 8431. OH OH iprMgBr,Ti(Oipr)4 Et20, rt OH 63% I.G.3-18 Yamamoto, Y. et al., JOC, 68, 2297. hex ~ hex

Pd(PPh3)4, dppf + Nuc-H

EtOH, 100~

~

hex x ~ he

Nuc 52-86%

I.G.3-19 Sanchez-Martinez, C.; Faul, M.M. et al., JOC, 68, 8008; Ferreira, E.M.; Stoltz, B.M., JACS, 125, 9578; Suffert, J. et al., OL, 5, 2307; Occhiato, E.G.; Prandi, C. et al., JOC, 68, 9728. H

H

O Pd(PPh3)4, KOAr DMA, reflux H

H 5-63%


95

I.G.3-20 Harada, T.; Kutsuwa, E., JOC, 68, 6716.

R'~

1. R23ZnLi, THF,-85~

R I ~

R2

2. ZnCI2, 02, TMS-CI "-

R'~O H 54-63%

I.G.3-21 Xi, Z. et al., JOC, 68, 4355; Oshima, K., JOC, 68, 6627. R

R ~

R

AICI3

ZrCp2 + R1-CHO

~--

R1

THF/Ph-Me,-78~ ~ rt

O 65-81%

I.G.3-22 Backvall, J.-E. et al., CEJ, 9, 3445 and JOC, 68, 7243. "Ailenes as Carbon Nucleophiles in Intramolecular Attack on (n-l,3Diene)-Palladium Complexes" Evidemce for trans Carbopalladation of the 1,3-Diene."

I.H.

Rearrangements v

I.H.1. Claisen, Cope and Similar Processes

I.H.I-1 Armstrong, A. et al., OBC, 1, 3142; Wang, J. et al., TA, 14, 891; Wee, A.G.H. et al., TA, 14, 897; Rainier, J.D. et al., TA, 14, 911. SX BocN~SX R ~ CH2C12,-40~-~ rt Boc "~ R1 R' EtO2C "CO2Et R 13-88% I.H.1-2 Blid, J.; Somfai, P., TL, 68, 3159; Tomooka, K. et al., TL, 44, 1239. 1-- R1 0 I

~

~

.n

O

NHBu

BBr3 ~

@

NHBu

NHBu 56-71%

96

ORGANIC SYNTHESISI2004

I.It.l-3 Anderson, C.E.; Overman, L.E., JACS, 125, 12412; Overkleeft, H.S. et al., EJOC, 2418. R2 R2 R['~~O

CH2C12,18h

k .Co " ~ ~

Ph~ph

b.~

R1N~ O

ipr

7-99% ee = 71-98%

Ph I.H.1-4 McComas, C.C.; van Vranken, D.L., TL, 44, 8203.

r.s+.j M e ,

Me

R*2NLi ~ M e @

THF, -78~ Me

Me 33-84% de = 20:1 ee - ___50%

I.H.1-5 Bio, M.M.; Leighton, J.L., JOC, 68, 1693; Karikomi, M. et al., TL, 44, 2167; Hana, I. et al., OL, 5, 1139; Cha, J.K. et al., AG(E), 42, 5044. T E S ~ 2 R~ TES R ~ ~ CO, pd(PPh3)4,EtNiPr2 OTf HO~ "~O Ph-CN, 80-100~ 1~2 R1

46-95%

I.H.1-6 Nelson, S.G. et al., JACS, 125, 13000; Motherwell, W.B. et al., SL, 805; Zhang, L. et al., TA, 14, 2195; Godage, H.Y.; Fairbanks, A.J., TL, 44, 3631; Florent, J.-C. et al., TL, 44, 4125; Eberlin, M.N.; Marsaioli, A.J. et al., JOC, 68, 5493. 1. [Ir(PCy3)2]+ CH2CI2/Me2CO OHL~~'~R2R~,,~'~R 1

2. 390C

R~~176 62-93% syn:anti = 11.5-49:1


97

I.H.1-5 Stoltz, B.M. et al., JACS, 125, 13624. O " ~

H

1

R

C,,"

I

AgOAc,TEA 2 THF,450C ~

R2 80-98%

I.H.1-6 Vogelsang, T.; Borschberg, H.-J., HCA, 86, 3583; Suzuki, H.; Kuroda, C., T, 59, 3157. q ' ~ N

Pd(PPh3)4'PPh3~

I.H.1-9 Cheng, H.-S.; Loh, T.-P., JACS, 125, 4990. O ~ l -~I "'~ "" In(OTf)3 or TfOH R-CHO + CH2CI2or hex

U/x

OH R~~'~

""

53-95% ee = 40-98%

I.H.I-10 Pietruszka, J.; Schone, N., AG(E), 42, 5638. Ph Ph BO~o h MeC(OEt):~EtCO2H~. ~ B ' O~ O j''Ph Me HO%, / / / . . . - - ~ , O ~ . . o M : 135~C , -.( .....XO"a-"~'OMe Ph ~ ]~hPh Y 64-76% I . H . I - l l Hong, J.H. et al., T, 59, 6103. O~ O B n TB S

~

~

1. TMS-CI,TEA,LHMDS,-78~ r t MeO2C,~OBn 2. Me-I, Triton-B, MeOH, rt

OBn

~l""~"~'l

OTBS OBn 82%

98


I.H.l-12 Nordman, G.; Buchwald, S.L., JACS, 125, 4978. R2

~4R3

O PhOe212o~ g~ ul se%__C-~~e

l~.,,~OH + R"

R4

g

Me- - ~ N~-'~N~----~Me

2

~

55-77%

I.H.I-13 Toyota, M.; Ihara, M. et al., H, 61, 133; Thomas, E.J. et al., TL, 44, 2713; Tsubuki, M.; Takahashi, K.; Honda, T.,JOC, 68, 10183.

~

~ 0 "

R

HO R R1 H

~

R1 BuLlor LDA THF, -78~

39-91% 1.7-7.3:1 I.H.I-14 Rainier, J.D. et al., JOC, 68, 993.

:- C~ SR

X

N2

SheOAc'4 CH2C12,rt

- 02R2

~:---~N&~ SR

H

75-98%

I.H.I-15 Davies, S.G. et al., CC, 2134.

"DoubleDiastereoselective[3.3]-SigmatropicAza-Claisen Rearrangement." !,H.2. Other Rearrangements I.H.2-1 Zard, S.Z. et al., OL, 5, 325. CO2H 1. (COCI)~CH2C12,rt

r

O~.o--CO2Et 2. c-C6HI:~reflux, h l ~ ~ ~ s ~

~C;

ONa

62%

O2Et


99

I.H.2-2 Maruoka, K. et al., JACS, 125, 3220. H

a-Np~~,~CHO /N RR

O

Ph-Me,-78 to -40~

~

I

.,L,I. R

f

~

OH

NIMe f

I.H.2-3 Shionhara, T.; Suzuki, K., S, 141. OH M , H ~ Ms-CI,TEA, AIEt3~ Ph CH2C12

62-94% ee = 78-97%

M

O ~

e k-

Ph

86-92%

ee = 99 % I.H.2-4 Bernard, A.M.; Piras, P.P. et al., OL, 5, 2923. O,

HH

OHH~.~~ CH2C12 81%

(R,S):(S,S) = 19:1 I.H.2-5 Tu, Y.Q. et al., OL, 5, 2319 and SL, 623, 1497 and CC, 798 and TA, 14, 2189. OH

X-

v

CH2C12, rt

X" v

i~ NHTs

96-98% syn:anti = 99:1

I.H.2-6 Hills, I.D.; Fu, G.C., AG(E), 42, 3921; Ruchirawat, S. et al., TL, 44, 1019.

1 O2R

Izt:

CH2C12, 35*C Ph

~~~h CN ~

oo

Ph =

88-98 % ee72-95%

100


I.H.2-7 Hurley, P.B.; Dake, G.R., SL, 2131. NBS iprOH,-78~

OH

Et

,Br r

rt

Et Ts

96% I.H.2-8 Jung, M.E. et al., OL, 5, 3159. OR OTES TMS.OTf,EtNiPr2 P r ~ Me Me

QTMS pr~~,_ CHO OR

CH2C12' .50~

Me Me 85-88%

I.H.2-9 Paquette, UA. et al., S, 1872. (

~OoBn KHMDS'18"Cr'6~" P h T H- F( , ~r t 41%

I.H.2-10 Pulido, F.J. et al., OL, 5, 4045.

ehoeeSi

R" v ~r~

CH2C12,0~

R1 68-82%

I.H.2-11 Shimizu, M.; Yamada, S. et al., BMCL, 13, 809. OMe OTBS ~ .

1. PdCI~ H20/dioxane . OBn 2. TBS-CI,DMF bBn

OBn OBn 84%

I.H.2-12 O'Brien, P. et al., TL, 44, 6613. NTs

SBuLi, sparteine

~- ~ N H T s

Et20, -780C ee

67% = 38%


101

I.H.2-13 Marson, C.M. et al., TL, 44, 141. Et SnBr4 ~

CH2C12 OH 65%

I.H.2-14 de la Moya Cerero, S. et al., JOC, 68, 1451; Martinez, A.G.; de la Moya Cerero, S. et al., TA, 14, 1607; see also: Ruedi, G. et al., OL, 5, 2691. o.

~ O

E+ rt '~ CH2C12, E 67-98%

I.H.2-15 McWhorter, Jr., W.W. et al., OL, 5, 333. HCO2H Ph-Me, reflux d / ~

r

NH Br

65%

I.H.2-16 Tius, M.A. et al., OL, 5, 4069. O Me(Y~'-

+ Ph

O

O 2. R-X, SiO2 46-89%

R

!1 OXIDATIONS II.A. C-O Oxidations

II.A.1. Alcohols-->Ketones , Aldehydes

II.A.I-1 Zhdankin, V.V.; Tykwinski, R.R. et al.,AG(E), 42, 2194; Quideau, S. et al., OL, 5, 2903; Natale, N.R. et al., SL, 2213; Rao, K.D. et al., JOC, 68, 2058.

q,,o R1

CDCI3, rt

R1 26-99%

NHR

II.A.1-2 Kim, S.S.; Borisova, G., SC, 33, 3961; Kim, S.S.; Kim, D.W., SL, 1391. R,,],.OH + PhlO -l- Mn(III)(salen)Cl ~ %0 Ar MeCN, 4~ MS, rt Ar 11-99% II.A.1-3 Bagherzadeh, M., TL, 44, 8943. IL~OH + Oxone Bu4NBr, H20/CH2CI2, rt R1 o ~ '~ /-~ CN"k o~,,, I,,o-~

I~O

R1 60-99%

II.A.1-4 Uozumi, Y.; Nakao, R., AG(E), 42, 194; Nagao, Y. et al., H, 61, 449; Guram, A.S.; Bei, X.; Turner, H.W., OL, 5, 2485; Sigman, M.S. et al., JOC, 68, 4600. IL~OH nano Pd eat., O2 1~O R1 H20, reflux R1 83-99%

102

OXIDATIONS

103

II.A.1-5 Sheldon, R.A. et al., CC, 2414; Miller, R.A.; Hoerrner, R.S.; OL, 5, 285; Kim, S.S.; Jung, H.C.; S, 2135. TEMPO, tBuOK R-CHO R,~R,,OH1 + CuBr2(2,2'-bipyridine) H20/MeCN,rt ~ 61-99%

II.A.1-6 Xu, L.; Trudell, M.L., TL, 44, 2553; Hajipour, A.R.; Ruoho, A.E., SC, 33, 871; Fernandes, R.A.; Kumar, P., TL, 44, 1275. R~OHR 1 +H5iO6+Cr(acac)3

,MeCN~ R~R10 20-96%

II.A.1-7 Yamaguchi, K.; Mizuno, N., CEJ, 9, 4353; Ciriminna, R.; Pagliaro, M., CEJ, 9, 5067; Katsuki, T. et al., SL, 1868; Springer, D.M. et al., BMCL, 13, 1751; Matsubara, S. et al., TL, 44, 9201; Uemura, S. et al., JOC, 68, 5875. 02 R~OH + Ru/AI203 ~ R~O R1 Ph-CF3 R1 71-99% II.A.1-8 Martin, S.E.; Garrone, A., TL, 44, 549; Ferguson, G.; Ajjou, A.N., TL, 44, 9139. ~OH R1

+ H202 4- FeBr3

MeCN or neat, 25~

R1 84.91%

II.A.1-90hsugi, S.; Node, M. et al., T, 59, 8398; Srinivas, P. et al., JOC, 68, 2460. "New Odorless Method for the Corey-Kim and Swern Oxidations Utilizing Dodeeyl Sulfoxide (Dod.S-Me)" II.A.I-10 Neumann, R. et al., JACS, 125, 5280. "A Water-Soluble and 'Self-Assembled' Polyoxometalate as a Recyclable Catalyst for Oxidation of Alcohols in Water with Hydrogen Peroxide" II.A.I-ll Bogdal, D. et al., T, 59, 649. I~OH R1

jaw

+ Mag treiveTu - - - - - - ~

R•RO1 41-99%

104


II.A.I-12 Ghorbani-Vaghei, R.; Khazaei, A., TL, 44, 7525. R1

~

CH2C12,-15~

TEA

R~R10 89-95%

II.A.I-13 Strazzolini, P.; Runicio, A., EJOC, 526.

R1--2~

II + HNO3 ~ ' ~ CH2C12

R1 0-94%

H.A.1-14 Hiroi, K. et al., JOC, 68, 1601. Ph H ~ R,,~OH +

/

Ph~o~ir ~

R-CHO

Me2CO or EtCOMe, rt~80~

33-96%

II.A.1-15 Kroutil, W. et al., JOC, 68, 402. R~OH R1

Rhodococcusruber Me2CO

R~O R1

-I-

R~,,,OH R1

conversion = 52-94 % ee = 10-99%

II.A.2. Alcohols, Aldehydes-->Acids, Esters II.A.2-1 Zanka, A., CPB, 51, 888; Giacomelli, G. et al., JOC, 68, 4999; Desai, R.N.; Blackwell, L.F., SL, 1981; Punniyamurthy, T. et al., TL, 44, 6033. R,,/OH

+ NaCIO + TEMPO

KBr H20/MeCN or EtOAr

~

R-CO2H 16-99%

II.A.2-2 Kita, Y. et al., SL, 723; Hiegel, G.A.; Gilley, C.B.; SC, 33, 2003; Forsyth, C.J. et al., TL, 44, 57; Taylor, R.J.K. et al., S, 1055. R,,./OH

+ PhlO or PDAIS

PDAIS = ~-I(OAc)2

' ~ MeOH/aq HCi, rt

R-CO2H 52-90%

OXIDATIONS

105

II.A.2-3 Borhan, B. et al., OL, 5, 1031; Patel, B.K. et al., JOC, 68, 2944. R-CO2R1 O x o n e R-CHO ~Oxone ~ R-CO2H 9-98% RLOH DMF 19-99% [similarly with V2Os] II.A.2-4 Karimi, B.; Rajabi, J., S, 2373. R1 + 02 + Co(OAe)2 OR 1

NHPI MeCN, rt

R-CO 2R 1 82-95%

II.A.2-5 Fang, X. et al., SL, 489. R

I~

CHO + NaCIO2 S~ 2

NaH2PO4

I ~RC O 2 H

H20/DMSO

S~ 2 52-96%

II.B.

II.B.1

C-H Oxidations

C-H--->C-O

II.B.I-I Yu, J.-Q.; Corey, E.J., JACS, 125, 3232; Nikolaropoulos, S.S. et al., ST, 68, 407; Velusamy, S.; Punniyamurthy, T., TL, 44, 8955. /---5 PO(OH)2/C, K2CO3 -I- tBuOOH ~ )n n CH2C12 ~

79-80% II.B.1-2 Kiuru, P.S.; Wahala, K., ST, 68, 373. OTHP LIDAKOR .~ THe

H

~

B(OMe)3, H202 THe t LIDAKOR = BuLl, tAmOKJiPreNtt/THF/Hex

99%

106


II.B.1-3 Momiyama, N.; Yamamoto, H., JACS, 125, 6038; MacMillan, D.W.C. et al., JACS, 125, 10808. R3SnO~.(R 3 BINAP.AgX O. R3 + Ph-NO ~ ~O-N-Ph Ri "R2 TI-IF, -78~ R1 R2 H 78-97% ee = 82-97 %

II.B.1-4 Lee, J.C.; Lee, Y.C., SC, 33, 3943; Curci, R. et al., JOC, 68, 7806; Demir, A.S. et al., TA, 14, 1489; Togo, H. et al., JOC, 68, 6424; Tanyeli, C.; Iyigun, C., T, 59, 7135. O O R ~ , , R 1 + TI(OTf)3

CH2Cl2,reflux ~

R~R 1 OTf 57-83%

II.B.1-5 Ishii, Y. et al., JOC, 68, 6587; Itoh, A. et al., S, 2289. x~.~ 02, AcOH, 25-100~ X . ~ ~ _ _ Me + Co(OAc)2 oi4 ~ CO2H O~,.N.~O

9-99%

HO"N"~N"oH O

II.B.1-6 Le Bras, J.; Muzart, J., TA, 14, 1911; Malkov, A.V." Kocovsky, P. et al., JOC, 68, 4727; Khan, K.M. et al., T, 59, 5549. Q CuI ~ Cull' cat" ~.~ + BzOOtBu

H20/(HOCH2CH2)20 ~

H

co2n

OBz

51-70%

ee = 34-42%

II.B.1-7 Schobert, R. et al., JOC, 68, 9827. CO2H 0

+ TBHP

0 2, hv CH2CI2, rt

O 60-72%

OXIDATIONS

107

II.B.2 C-H'C-Hal II.B.2-1 Montoro, R.; Wirth, T., OL, 5, 4729. "Direct lodination of Alkanes"

II.B.2-2 Massanet, G.M. et al., TL, 44, 6691. Me CeCIy7H20 + NaCIO H20/CH2CI2 R~ ...

~,,tC 1 60-98%

II.B.2-3 Togo, H.; Hirai, T., SL, 702. (BzO)2or AIBN Ar-Me + NBS ..... ionic liquid or neat

Ar~Br 21-89%

II.B.2-4 Stavber, S. et al., S, 853. O n_.~~Me (NO)

O

MeOH, rt

+ I2

(RO)n___~~ ''~''sl

F-N+ L.JN+-CHeCI03F4)2 II.B.2-5 Ghorbani-Vaghei, R., TL, 44, 7529. [TS'N__~ TFAA ~ Rx'--l"-~

+

1"

"~2 MeCN-

70-91%

R(3--1 90-93%

II.B.2-6 Corelli, F.; Botta, M. et al., S, 1039. "Microwave-Assisted C-5 Iodination of Substituted Pyrimidinones and Pyrimidine Nucleosides"

II.C C-N Oxidations

II.C-1 An, G.; Rhee, H., SL, 876; Rhee, H. et al., SL, 112. O B n . ~ BF3"Et20 B n . ~ + MCPBA CH2CI2, rt X

62-83%

X

108


II.C-2 Nicolaou, K.C. et al., AG(E), 42, 4077; Kocevar, M. et al., S, 2349. R,,N..,~R1 + IBx ,~ R,,I~R1 H DMSO, 450C 49-98% II.C-3 Zolfigol, M.A. et al., SL, 933. R"I~R1

+ UHP

maleic anhydride

MeOH, 0~

R-'R1 80-95%

II.D. A m i n e O x i d a t i o n s

II.D-1 Wang, Y. et al., SC, 33, 1781. H Ph""~"~N"N'Ar + NaBrO3

Ph N Ar H2SO4

n

O 74.86%

II.D-2 Licini, G. et al., TL, 44, 49. R1 R3.OOH Ti(Oipr)* CHP' 4A MS R,J'~ N-.R2 4H CHCI3, 60~

R~IN+R 2 O" 45-98%

II.D-3 Phanstiel, IV, O. et al., T, 59, 4315. R-NH2 + BPO

R,.N.OBz CH2Cl2/buffer

H

74-90% II.D-4 Jain, S.L.; Sain, B., AG(E), 42, 1265. RI~ CoII Sehiff base complex, 02 R,,N,,R2 DCE, 5A MS, 20~

R1 i ,,O

50-92%

II.D-5 Sain, B. et al., TL, 44, 3235. R/~---NH2

+ MeRuO3

MeCN, reflux

R/x~--NO2 89-92%

OXIDATIONS

109

II.D-6 Rassat, A.; Rey, P. et al., CC, 2722. "A Versatile Synthesis of N e w P y r i m i d i n y l Nitronyl Nitroxides"

II.D-7 Doris, E.; Mioskowski, C. et al., TL, 44, 6591. "Ph3BiCO3: A Mild Reagent for in situ Oxidation of Urazoles to Triazolinediones" II.D-8 Chen, F.-E. et al., S, 2629. RANH2

+ TCCA

TEMPO

R-CN

CH2CIz, 10*C

80-91%

II.E. S u l f u r O x i d a t i o n s

II.E-1 Akamanchi, K.G. et al., JOC, 68, 5422. R.. TEAB S + IBX ~1 H20/CH2CI2, rt 90-98% II.E-2 Aggarwal, V.K. et al., JOC, 68, 4087.

,o

1

+ Ph%oOHMe Ti(Oipr).DET . C~_ ]R1 Me

CH2C12,-40 to -20~

"o 60-75% ee = 98-99 %

I.E.3 Kim, S.S.; Rajagopal, G., S, 2461; Miyazaki, T.; Katsuki, T., SL, 1046; Saikia, A.K.; Chaudhuri, M.K. et al., TL:, 44, 4503; Begue, J.-P. et al., OS, 80, 184. Crmsalen R,, S,,,,O R'S + Ph-IO ~ ~1 CH2C12, rt ~1 64-99%

II.E-4 Weix, D.J.; Ellman, J.A., OL, 5, 1317. tBu~S~ S,'tBu + H202

VO(acac)

Me2CO, 0~

O II tB~,-S~ StBu 98% ee = 86 %

110


II.E-5 Zen J.-M. et al., AG(E)i 42, 577. "An Efficient and Selective Photocatalytic System for the O x i d a t i o n of Sulfides to Sulfoxides"

II.E-6 Legros, J.; Bolm, C., AG(E), 42, 5487; Bradley, M. et al., OL, 5, 235; Thakur, V.V.; Sudalai, A., TA, 14, 407; Linden, A.A.; Kruger, L.; Backvall, J.-E., JOC, 68, 5890. CH2C12, rt ,O R.,.S -i- H202 ~ R., S .... 21-44 %

H

ee = 27-90%

II.E-7 Choudary, B.M. et al., CC, 754; Trudell, M.L. et al., JOC, 68, 5388; Finley, K.T. et al., JOC, 68, 4988. O2 R" s + LDH-OsO4 .1~ R~SO2 ~1 tBuOH, burrer R1 95-99%

LDH = layered double hydroxide II.E-8 Mohammadpoor-Baltork, I. et al., SC, 33, 953; MohammadpoorBaltork, I.; Khodaei, M.M.; Nikoofar, K., TL, 44, 591. R1 S R1 .O R.%2

+Oxone

neat ~

I~N'-~R2 73-99%

II.F. Oxidative Additions to C-C Multiple B o n d s

II.F.1 E p o x i d a t i o n s

II.F.I-1 Kuhn, F.E.; Romao, C.C. et al., OM, 22, 2112. "A Simple Entry to ( s-CsRs)chlorodioxomolybdenum (Vl) Complexes (R = H, CH3, CHzPh) and their Use as Olefin Epoxidation Catalysts" II.F.1-2 Stack, T.D.P. et al., OL, 5, 2469. I((phen)2(H20)FeIII)2(~t-O)lCIO4 R

AcOH/MeCN, 0~ 85-96%

OXIDATIONS

111

II.F.1-3 Rozen, S.; Golan, E., EJOC, 1915.

R1

R2

R

R3

R)LQ~RI HOF, MeCN

R

R"

70-95%

F2, H2O, MeCN II.F.1-4 Sartori, G.; Armstrong, A. et al., JOC, 68, 3232. R1 R2 KG-60-FT, Oxone R~ R

Na2EDTA, NaHCO3, H20/MeCN

R2

R 93-99% ee = 48-80%

KG-60-FT= (x-fluorotropinoneon SiO2

II.F.1-5 O'Neill, P.M. et al., TL, 44, 8135; Iqbal, J. et al.,JOC, 68, 1679. R1 R2 C(Tthd)2,02 R~L~R2 / \, R tBu-CHO R R~ 70-95% II.F.1-6 Chandrasekaran, S. et al., T, 59, 7761; Beller, M. et al., TL, 44, 7479. ipr-CHO, 02, NaHCO3, CH2C12 )n

'

)n f--~

o "~

56-80%

~

,~ 9 ,~ I N ~ O

I I . F . 1 - 7 0 n a k a , M. et al., OL, 5, 85; see also: Shibasaki, M. et al., AG(E), 42, 4680; Sasai, H. et al., TA, 14, 1587; de la Pradilla, R.F. et al., JOC, 68, 4797; Yamamoto, H. et al.,AG(E), 42, 941; Zhang, R. et al., JOC, 68, 1721, 8222; Lattanzi, A. et al., CC, 1440 R R 1 CHP, Zr(OtBu), OBTA ,R , g1 H (~~R --

2

Ph-CI

~

H ~(~/~o

R2

55-98% ee = 47-87%

112


I.F.1-8 Shi, Y. et al., OS, 80, 9; Bez, G.; Zhao, C.-G., TL, 44, 7403; Shing, T.K.M. et al., TL, 44, 9225. R1

R2

Oxone, KOH, DME/MeCN

R~

9

R2

71-93%

ee = 90-98% I I . F . 1 - 9 0 ' B r i e n , P. et al., OL, 5, 4955; Curci, R. et al., SC, 33, 3009; Sun, Y.-C.; Chen, K. et al., JOC, 68, 9816; Solladie-Cavallo, A.; Bovicelli, P. et al., TL, 44, 6523. "cis- and trans-Stereoselective Epoxidation of N-Protected 2Cyclohexen-l-ylamines" II.F.I-10 Zhang, R. et al., OL, 5, 725; Vogl, N. et al., TA, 14, 1355. R 1 R2 [ZnW(VO)2(ZnW9034)2] "12 R1 R2 \m/ k___/

R / ' ' ' ~ OH

~

Rf"~ ~ OH

TADOOH TADDOL N~..~

82-96% er = 19:1

I I . F . I - l l Liang, X. et al., CC, 2714; see also: Murphy, P.J. et al., TL, 44, 8677.

9

o

R

aq KOH, Ph-Me

R1 + cU " ( I!

o

p..-

OO

R2

74-97% ee = 64-96%

II.F.I-12 Stack, T.D.P. et al., JACS, 125, 5250. "Efficient Epoxidation of Electron-Deficient Olefins with a Cationic Manganese Complex" II.F.I-13 Kumaraswamy, G. et al., TA, 14, 3797. "Enantioenriched (s)-6,6'-DiphenylBinol-Ca: A Novel and Efficient Chirally Modified Metal Complex for Asymmetric Epoxidation of ~,13-Unsaturated Enones"

OXIDATIONS

113

II.F.l-14 Taylor, D.K. et al., JOC, 68, 5205. R~._R1

MCPBA CH2C12,rt

R - ~

R1

O 51-93% de = 26-100% II.F.2 Hydroxylations II.F.2-1 Choudary, B.M. et al., JOC, 68, 1736; Chandrasekhar, S. et al., CC, 1716; Percy, J.M. et al., OL, 5, 337; Beller, M. et al., S, 295; Jonsson, S.Y.; Adolfsson, H.; Backvall, J.-E., CEJ, 9, 2783; Hattori, K. et al., BMCL, 13, 4277; Ghosh, A.K.; Kim, J.-H., TL, 5, 3967; Hartung, J. et al., SL, 51; Marcune, B.F. et al., JOC, 68, 8088. DH 1. LDH-PdOsW, TEA Ar~R Ar-X + ~ R , ~.2. (DHQD)2PHAL,NMM, H202 ()H iBuOH/H20

82-93% ee = 47-99%

II.F.2-2 Morken, J.P. et al., JACS, 125, 8702; Plietker, B.; Niggemann, M., OL, 5, 3353; Huang, J.; Corey, E.J., OL, 5, 3455; Evans, P.; Leffray, M., T, 59, 7973; Friedrich, H.B., et al., CC, 2922; Muniz, K.; Nieger, M. et al., OM, 22, 4616. R1

R2

R

R3

( n o r b o r n a d i e n e ) R h ( a c a c ) , TttF, rt

OH 17-76%

R

ee = 3 3 - 9 8 % PPh~

II.F.2-3 Sato, K. et al., AG(E), 42, 5623. "Catalytic Dihydroxylation of Olefins with Hydrogen Peroxide: An Organic-Solvent- and Metal-Free System" II.F.2-4 Li, Z. et al., JOC, 68, 8599; Muller, M. et al., CEJ, 9, 4188. Enantioselective trans Dihydroxylation of Nonactivated CmC Double Bonds of Aliphatic Heterocycles with sphingomonas sp. HXN-200"

114


II.F.2-5 Lohman, G.J.S.; Seeberger, P.H., JOC, 68, 7541; Knochel, P. et al., CEJ, 9, 5259. ~ , _.~ (RO)3

DMDO, ZnCI 2 ~ CH2CI2, 0IJC

=/

R

),,,t/

H20/Ph-Me, rt

R

55-94% ee = 66-94 % josiphos = 1-[(2-diphenylphosphanyl)-

ferrocenyl]ethyldicyclohexylphosphine III.E.1.3 Rampf, F.A. et al., CC, 2210; Hoge, G., JACS, 125, 10219; Bakos, J. et al., TA, 14, 1087; Kissel, W.S. et al., JOC, 68, 5731; Zhang, M. et al., OL, 5, 1587 and AG(E), 42, 943; Imamoto, T. et al., TA, 14, 2171; Nakano, D.; Yamaguchi, M., TL, 44, 4969; Bakos, J. et al., TL, 44, 9025. R1 HN-Ac H2,[Rh(cod)2]OTf,CH2CI2,rt R1 HN-Ac 64-99% ee = 8-96 %

III.E.1-4 Beletskaya, I.P.; Pfaltz, A. et al., TA, 14, 1397; Knochel, P. et al., AG(E), 42, 3941; Cozzi, P.G. et al., SL, 833; Burgess, K. et al., JACS, 125, 113; H2, [Ir(cod)(lig)]+(BAr4)", CI-12C12,rt Me AAP(OEt)2 ~ Ar'~P(OEt)2 o

o (Me'Ph)2P

82-99%

ee = 70-94 %

126


III.E.1-5 Li, X.; Chan, A.S.C. et al., JOC, 68, 4539; yeung, C.H.; Chan, A.S.C. et al., TA, 14, 987; Weberskirch, R. et al., CEJ, 9, 3228; Mikolajczyk, M.; Chauvin, R. et al., OM, 22, 4810; Sajiki, H.; Ikawa, T.; Hirota, K., TL, 44, 8437; Beller, M. et al., JOM, 675, 91; Evans, D.A. et al., JACS, 125, 3534; Doherty, S. et al., TA, 44, 1517; Ward, T.R. et al.,JACS, 125, 9030 A ~ C O 2 M e H2, [Rh(cod)2BV4l,Tar, r t Aff~,CO2M e NHR

~

NHR 100% conversion ee = 96-99%

Op_NEtz o

III.E.1-6 Zhang, X. et al., AG(E), 42, 3509 and JACS, 125, 9570; Yeung, C.; Chan, A.S.C. et al., JOC, 68, 2490; Minnaard, A.J.; Feringa, B.L. et al., OBC, 1, 1087; Holz, J.; Borner, A. et al., JOC, 68, 1701 MeO2C~HN-Ac H2, Rh-binapine ~,- MeO2Cx,,,,~N'Ac Ar

THF, rt

Ar 99% ee = 96-99%

III.E.1-7 Giri, V.S. et al., S, 1549; Buchwald, S.L. et al., JACS, 125, 11253. O ~ O R

PPh3

MeOH ~ O ~ ~

R

O

55-75% III.E.1-8 Firouzabadi, H.; Iranpoor, N.; Alinezhad, H., BCJ, 76, 143. {[~.-CX Zr(BH4)2CI2(DABCO)2'Na(BH3CN).-- ( ~ ~ - C X ZnCI2, MeOH, A 82-91% (similarly for imines, reductive aminations) III.E.1-9 Ranu, B.C.; Samanta, S., JOC, 68, 7130 and T, 59, 7901; see also: Yamada, T. et al., TA, 14, 967. Rl NaBH4,InO3 ~. R,.,.~,,,,,,~R 1 MeCN, rt 77-97% [also with tx,~unsaturated ketones]

REDUCTIONS

127

III.E.I-10 Lee, H.-Y.; An, M., TL, 44, 2775. R1

O

R~3

R1 R2

C~ H20 ~ DME. reflux

O

RR ~ ~ 3

R2

0-99% III.E.I-ll Reetz, M.T.; Goosen, L.J. et al., OL, 5, 3099; Boulton, L.E. et al., OBC, 1, 1094; Vankelecom, I.F.J. et al., CEJ, 9, 334; Zheng, Z.; Chen, H. et al., OL, 5, 4137; Ojima, I. et al., OL, 5, 3831; see also: Lennon, I.C.; Pilkington, C.J., S, 1639. "Enantioselective Rh-Catalyzed Hydrogenation of Vinyl Carboxylates with Monodentate Phosphite Ligands." III.E.I-12 Ager, D.J.; Prakash, I., OPRD, 7, 164. ~ ~ ~ "CO2H H2, R h / C ~~b~ NH2 ~ ~

cO2H NH2

81-97%

III.E.2 C-C Reductions

III.E.2-1 Tsuji, Y. et al., CC, 2820. 1. Ti(Oipr)4, BuLl, THF, -78~ R

~

R

2. H3O+

90-99%

III.E.2-2 Huang, X. et al., JOC, 68, 1958. 1. Cp2Zr(H)CI, THF, rt R ~ Ts 2. E +

III.E.2-3 Wu, M.-J. et al., TL, 44, 1979. Pd(OAc)2, NaOMe R

~

R1

R1

R1

MeOH

R r

,_/ R

0-92%

E Ts 40-72% E:Z = 9.2-99:1

R1

R

R1

+ 0-50%

128

III.F.


Hetero Bond

Reductions

III.F.1. C-O --->C-H

III.F.I-1 Merschaert, A. et al., TL, 44, 4531; Kolis, S.P. et al., TL, 44, 5707. Me Ar Me OH Me Boc,, -~ Boc,, r Boc,, r EtOH Ph-Me, 100~ 52% 4.5:1 85% 24:1 III.F.1.2 Lautens, M.; Paquin, J.-F.; OL, 5, 3391. O OPG O OPG ~ O C O 2 R 3 Pd(OAc)2'Bu3PHBF4 ~._ HCO2H/TEA,MeCN,40*C- R ~ 60-89% dr = 1.4-20:1 III.F.1-3 Crich, D.; Yao, Q.; OL, 5, 2189; Dang, H.-S. et al., OBC, 1, 1330. I BnO

Bu3SnH, AIBN .~ B z O . ~ O ~ o R Ph-Me, reflux BnO--x~ -

~

74-80%

III.F.1-4 Deniau, E. et al., TA, 14, 2253. O ~ R

~MN-

O

Et3SiH,TFA ~ ~ I N . _ ~ CH2C12,-78~ -' rt e

III.F.1-5 Haldar, P.; Ray, J.K., TL, 44, 8229. EtO2 NaBH, I2 ~ EtO2 EtO2C~ ~ O THF - EtO2C~N/ Ar Ar 77-84%

'OMe 62-92%

REDUCTIONS

129

I I I . F . 1 - 6 0 h t a , T. et al., CC, 1192. 3 2 1. PhSiH3, RhCI(PPh3)3 R ~OR OR R1

2. aq

NaOH

R ~ O R2 R1 64-91%

III.F.2. C-Hal --> C-H

III.F.2-1 Nishiyama, Y.; Sonoda, N. et al., T, 59, 6609. "Dehalogenation of o-Dihalogen Substituted Arenes and a,a'Dihalogen Substituted o-Xylenes with Lanthanum Metal." III.F.2-2 Hilmersson, G.; Flowers, II, R.A. et al., JOC, 68, 4870. "Rapid Sml2-Mediated Reductions of Alkyl Halides and Electrochemical Properties of Sml2/H20/Amine." III.F.2-3 Kadota, I.; Yamamoto, Y. et al., TL, 44, 8645. R~.~.I Zn-Cu, AcOH ~ R,,.~.~I I MeOH/THF 74-95% cis:trans = 100-1:1-3 III.F.2-4 Wang, L. et al., SL, 1137. Ar~,,,Br Sm Br MeOH,45~

R - " ~ rBr

95-98% Z:E = 1:1.5-3.5 (also further reduction to alkenes and alkanes)

III.F.2-5 Taillefer, M.; Cristau, H.-J. et al., TL, 44, 7191. X~__ N2H4"HCI'Pd/C' NaOH R ~ R Ph-Me, rt 42-99% III.F.2-6 Yus, M. et al., T, 59, 1237. R-F + ~ T M S " ~ "TMS

Li, DTBB

R-H 28-86%

130


III.F.3. C-S --->C-H

III.F.3-1 Boivin, J. et al., OL, 5, 1645. o H3PO2, AIBN, TEA SO2Ph

O

(EtO)2PH(O)

~SO2Ph 49-89%

S III.F.3-2 Petrini, M. et al., SL, 1129. RL SOzPh NaBH3OAc ~R1 H

dioxane,reflux

R~N

-',, R 1 H

68-96% III.F.3-3 Yoda, H. et al., SC, 33, 1087. o o

o

Sm'

Ph THF, rt R (O)n

6-68%

(also for iactams)

III.G. Reductive Cleavages

III.G.1. Oxiranes

III.G.I-1 Concellon, J.M.; Bardales, E., OL, 5, 4783; Ikariya, T. et al., OM, 22, 4190. o R ~ R I NR2R3 S m I 2 R ~ _ O MeOH '~ NR2R3 R1 62-80% III.G.1-2 Yu, J.-Q. et al., OL, 5, 4665. "Recyclable Polyurea-Microencapsulated Pd(0) Nanoparticles: An Efficient Catalyst for Hydrogenolysis of Epoxides."

REDUCTIONS

131

III.G.1-3 Concellon, J.M. et al., JOC, 68, 1585. R2 R2 R ~ C O 2 R 3 1. SmI2,THF, reflux R~RD1CO2R3 2. D20 R1 49-85%

III.G.1-4 Tu, Y.-Q. et al., CEJ, 9, 4301. OH ~]~ SmI2 ~ ~ OCOR1 O + RI'cHO - N,~,~O" ' r'H R DCE, rt~ 70~

~ _ O~HcoR1 R

R

0-62% 1.5-99:1 III.G.1-5 Mal, D. et al., TL, 44, 2355. .,j(?~[j~ R2 O R-

"~.

R1

Mo(CO)6 A ~ R2t~ ~'~ R3

Ph-H or Ph-Me,

"

R3

'R1

0-96% III.G.1-6 Howell, A.R. et al., JOC, 68, 1480. h/~O Nuc-TMS,T B A ~ p h ~ p CH2C!2

~Nuc OH 27-90%

III.G.2. N--O Cleavages III.G.2-1 Demitz, F.W.J. et al., TL, 44, 8217. R ~'w"q Ni~ Zn anode R ~ O H e

§

R~OH

R" "CO2Me R" "CN 23-99% 1:100-13:1

132


III.G.3. Other Reductive Cleavages

III.G.3-1 Faucher, A.-M.; Grand-Maitre, C.; SC, 33, 3503. l~s,,.O P(CH2CH2CO2H)3 ~_ R'- S

kl

k'

98-99% (similar reductions of sulfonyl chlorides, N-oxides and azides)

III.H. Reduction of Azides

No Entries

III.I. Other Reductions

III.I-1 Gosmini, C. et al., TL, 44, 6417. " N e w Progress in the Cobalt-Catalysed Synthesis of Aromatic Organozinc Compounds by Reduction of Aromatic Halides by Zinc Dust." IIl.l-2 Shuto, S. et al., JOC, 68, 9155. Ph i.~

I,.IL...IL

t~'N"~OTBDPS S O

TMS3SiH, Et3B or AIBN "" ~" eh ~,,~',~"~OTBDPS ' THF or Ph-H 22-80% cis:trans = 2.5-14:1

III.I-3 Caddick, S. et al., T, 44, 5417. NiCI2.6H20, NaBI-I4,Boc20 R-CN MeOH

R ~ N -B~ H

21-96% III.I-4 Zhang, C.-R.; Wang, Y.-L., SC, 33, 4205. O O R.J~N~N,,Ar N2H4.H20~ R.,U.,N.N~ArH EtOH H 69-91% (similar reduction of azo compounds)

IV SYNTHESIS OF HETEROCYCLES IV.A. Oxiranes, Aziridines and Thiiranes

IV.A-1 Aggarwal, V.K.; Lee, H.-Y. et al., AG(E), 42, 3274; Forbes, D.C. et al., OL, 5, 2283; Ciaccio, J.A. et al., SC, 33, 2135; Metzner, P. et al., S, 2249. R~O ' ~ R1

+

,O~R2

~N~BF4"

f,\.,S+~R2 KOH or phosphazene b a s e

R,,

~

R1

Q ~

37-93% dr = 1.7-99:1 ee = 71-99%

IV.A-2 Bacieredo, A.; Branchadell, V.; Ortuno, R.M. et al., JOC, 68, 7707. R1

CHO +

--vR2

THF, rt

~

R1

\/', O PR2 S 65-87%

IV.A-3 Che, C.-M. et al., TL, 44, 5917. n

R

~

H 2

PhIO,Rh2(4S-MEOX)4, Al203 Ph-H, 5"C

R

~ 02 68-95% ee = 55-76%

IV.A-4 Cui, Y.; He, C., JACS, 125, 16202; Suga, H. et al., BCJ, 76, 189. R1 R1 AgNO3, tBu3tpy ~- R~~~N~R2 R-~ R 2 + PhI=NTs MeCN I

Ts 66-91% (similar chemistry using Cu catalyst) 133

134


IV.A-5 Tang, Y. et al., CC, 2074; Linclau, B. et al., JOC, 68, 8252.

R-CHO -I- B r f " ' ~ R 1

K2CO3

~

tetrahydrothiophene/tBuOH, reflux

R1 75-96% cis:trans = 1:3-1.22:1

IV.A-6 Lindsay, Smith, J.R.; Reginato, G., OBC, 1, 2543. "Asymmetric Alkene Epoxidation Catalyzed by a Novel Family of Chiral Metalloporphyrins: Effect of Structure on Catalyst Activity, Stability and Enantioselectivity." IV.A-7 Vedernikov, A.N.; Caulton, K.G., OL, 5, 2591; Hutchings, G.J. et al., CC, 2808; Kantam, M.L. et al., TL, 44, 9029. "Angular Ligand Constraint Yields an Improved Olefin Aziridination Catalyst." IV.A-8 Jain, S.L.; Sain, B., TL, 44, 575; Thakur, V.V.; Sudalai, A., TL, 44, 989.

R1 R%

R1 CuCI, 5A MS,~ R ' ~ , , R2 R2 + TsNIK MeCN ~? k 3 Ts 40-80%

IV.A-9 Katritzky, A.R. et al., JOC, 68, 407.

R~O LDA .~. B t ~ R + Bt-CH2C! R1 THF, -78~ Rx 62-75% IV.A.10 Loreta, M.A. et al., TL, 44, 4953. R

~ 2

R

1

?O2~21 EtO2CNHONs,CaO CH2C12

39-60% IV.A-11 Alves, M.J. et al., TL, 44, 6277. "Optically Active Aziridine Esters by Nucleophilic Addition of Nitrogen Heterocycles to a Chiral 2H-Azirine-2-Carboxylic Ester."

SYNTHESIS OF HETEROCYCLES

135

IV.A-12 Aggarwal, V.K.; Vasse, J.-L., OL, 5, 3987. ( P h Rh2(OAc)4~PTC, dioxane, 40~

~I~SE

+ TS,,N. N S Na

%•PsEs

, ~ ~,

52% dr = 8:1 ee = 98 %

Iu Yadav, J.S. et al., TL, 44, 5275 and S, 1387; Bergman, R.G.; Tilley, T.D. et al., JOC, 68, 9705. Ar LiCIO4 A R-CHO + Ar-NH2 + N2CHCO2Et MeCN, rt R CO2Et 75-91% cis:trans = 4.55-100:1 IV.A-14 De Kimpe, N. et al., TL, 44, 1137.

,J NaOMe

OMe

~ , ] I I , , .

R- ~ "

MeOH, A

R51-85%

IV.A-15 Davis, F.A. et al., JOC, 68, 6894, 2410. D I LiI-IDMS r" M e ~ ~" ~ Ph-X + O~P(OEt)2 THF, -78~

X-Ph",~ 'P(OEt)2 S, O (3)" Mes 72-82%

IV.A-16 Katritzky, A.R. et al., JOC, 68, 9105. HO.,N

RI~B t

Ts-CI,aq KOH

~Bt R" 58-66%

IV.A-17 Kazemi, F.; Kiasat, A.R.; Ebrahimi, S., SC, 33, 595. R (NH2)2CS,LiBF4 R MeCN, reflux 80-96%

136


IV.A-18 Stockman, R.A. et al., SL, 1985. D Nail tBu~X,N~R + Me3S+[" DMSO, rt

~"'7"7,

NI R

O'%u 63-84%

de = 77-95%

IV.A-19 Filippone, P.; Stanovnik, B. et al., SL, 995. Hz RO2C,N ~ . ~ O 2 R I + ~ CO2Me .. Me2N-~CO2 Me Ph.Me, reflux~ HN"~"~CO2 R1 Me NHBz RO2C Me 51-70% IV.A-20 Hashimoto, M.; Matsumoto, M.; Terashima, S., T, 59, 3041, 3019, 3063, 3089; Fernandez-Bolanos, J.G.; Bolf, M. et al., OBC, 1, 478; Schirmeister, T. et al., TA, 14, 3301.

Bn~..OBn O~~c~OEE Ms

Bn t

,.OBn

KHMDS.1~ THF, 60~

C ,OCo2Et 2Et 63%

IV.A-21 Suarez, E. et al., OL, 5, 3729; Somfai, P. et al., TL, 44, 5339; Gudmundsdottir, A.D. et al., TL, 44, 6763; Alajar~, M. et al., S, 49.

OR A_ c O ~ ~ OHCO

N3

OR Ph.Me,reflux~ A_ _ ~ OHCO 63-85%

IV.A-22 Palacios, F. et al., TA, 14, 689. TSO'N O R"n(OEt)2.~/r II

K2CO~chiral base Ph-H, rt

~-

o,

~P(OEt)2

R~ 49-97% ee - 2-72%

SYNTHESIS OF HETEROCYCLES

137

IV.A-23 Yadav, J.S. et al., SL, 396; Salehi, P.; Khodaei, M. et al., SC, 33. 3041. R InBr3 R ~ R 1 +KSCN MeCN, A ~ ~-S-S-S~R 1 80-95% IV.B. Oxetanes, Azetidines and Thietanes

IV.B-1 Shi, M. et al., OL, 5, 4737. /COY DABCO,4A MS Ar'~NTs + --- " Ph-H ~

/~___/COY Ar"~Nf Ts 42-99%

IV.B-2 Couty, F. et al., SL, 726. c02Et CN Li.o

Bn

.=--CO2Et S

~

THF, -78~

CN Bn 58-73%

IV.B-3 Jiang, J. et al., OL, 5, 4101. "Synthesis of 4-Trifluoromethylated 2-Alkyl and 2,3-DialkylSubstituted Azetidines." IV.B-4 Sakamoto, M. et al., CC, 2218. "Diastereoselective Photocycloaddition of Axially Chiral Monothiosuccinimides to 1,1-Diphenylethylene."

IV.C. Lactams IV.C- 1 Lautens, M. et al., JACS, 125, 4028. Ar O ~ N H + Ar-CH=X MgI2 THF I

Ar

Ar 38-81%

138


IV.C-2 Perlmutter, P. et al., EJOC, 756; Danheiser, R.L. et al., OS, 80, 160; Lectka, T. et al., SL, 1937; Tavani, C. et al., T, 59, 10195; see also: Williams, R.M. et al., OL, 5, 2095. O ,-"~,, "Ph SnCl4, TEA ~ r 4N~"'~Ph C12C12

Me~"ph

25-79% IV.C-3 Shintani, R.; Fu, G.C., AG(E), 42, 4082. / CuBr,Ph(TMSO)C=CH~ KOAc + Me

-0- l~Ar

O~

Me. ICeMe Me~

70% ee = 90%

Me Me

IV.C-4 Tang, Y. et al., CC, 2554; Cordero, F.M.; Salaun, J.; Brandi, A. et al., JOC, 68, 3271; Jimenez, J.L. et al., JOC, 68, 6338; Alcaide, B.; Almendros, P. et al., JOC, 68, 1426; Alcaide, B. et al., JOC, 68, 3106.

R

R1

Cu(CIO4)2"6H2O, cy2NH,ipr-trisoxazoline

IIll + "O"~'R 2

'

/N~ iipr

39-63%

ee = 55-82% ~Pr

IV.C-5 Ryu, I.; Komatsu, M. et al., JACS, 125, 5632. Bu3SnH, AIBN, CO

n

Ph-H

Bu3Sn~)

(~~R 61-88%

IV.C-6 Gottlich, R. et al., S, 1886.

O~~~ 1 R

R1

O~'-k R2

OR

V.E-17 Sajiki, H.; Hirota, K. et al., TL, 44, 7407. "Significant Supplier-Dependent Disparity in Catalyst Activity of Commercial Pd/C Toward the Cleavage of Triethylsilyl Ether" V.E-18 Sarm, J.C.; Tsuboi, S. et al., SC, 33, 4005. ~tw TBDMS-CI or TMS-CI, 12 R1-OH r.-- R1-OSiR3 neat 63-96

V.F. Other Protecting Groups

V.F-1 Corey, E.J. et al., OL, 5, 1999. Me

N.--~O + %NMe H

CH2C12,0*C, lmin 58-99% -4

A, lmin 65-99%

V.F-2 Stuhr-Hansen, N., SC, 33, 641. AcCI, BBr3 Ar-SAc -~ Ar-S.tBu 89-96% CH2CIz/Ph-Me,rt, 2h V.F-3 Kilburn, J.D. et al., JOC, 68, 9416. "Trifluoroacetyl as an Orthogonal Protecting Group for Guanidines"

Vl USEFUL SYNTHETIC PREPARATIONS VI.A. Functional Group Preparations VI.A.1. Acetals and Ketals

u

Vyvyan, J.R. et al., JOC, 68, 9144. R,~

SnCI2 Me2CO,reflux r

S

48-97%

VI.A.1-2 Read, R.W.; Zhang, C., TL, 44, 7045. "Synthesis of Fluorons Acetal Derivatives of Aldehydes and Ketones" VI.A.1-3 Kurihara, M.; Hakamata, W., JOC, 68, 3413. R~O + ~~ R2"OTMS'TMS'OTf ~ ~ROI~ R1 ~ CH2CI2,-20"C 70-99% VI.A.1-4 Feringa, B.L. et al., JACS, 125, 8714. ~O o ~ O Pd(OAc)2,p(OPh)3 ~ 0 R-OH + R1 CH2C12,"30~ RO" 57-98% ee = 82-99% VI.A.1-5 Miller, S.J. et al., SL, 1923. OBn . H~nO.[ ~ j ~ , _O Bn + R'~oHR CH2CI2,4AMS, rt CI3CAOe' "O" "~ OBn

~ a

225

OBn .L ,OBn ~BnO".[~-~]~.'R ~ O ~'' 28-92t~~ OBn

s~ 2 N"~CO~e ~A~~

226


VI.A.1-6 Nishida, Y.; Kobayashi, K. et al., OL, 5, 2377. "One-Pot r Method Using Appel Agents in N,NDimethylformamide" VI.A.1-7 Stachulski, A.V. et al., OL, 5, 4545; and see also: CC, 1266. "Giycosidation with a Disarmed Glycosyl Iodide: Promotion and Scope" VI.A.1-8 Bertozzi, C.R. et al., OL, 5, 3185. "Formation of 1,1-~#-Glycosidic Bonds by Intramolecular Aglycone Delivery. A Convergent Synthesis of Trehalose" VI.A.1-9 Zhang, J. et al., OL, 5, 5015. X

X

R2 OR +

"-'R 1 H(I

v

X

X

/

CsF ~ CH2CI2, rt

R2 --R 1

70-91% (also amidations)

VI.A.I-10 Takashi, T. et al., AG(E), 42, 1833. SMe

5

+

CH2C12, 4/~ MS

()Bn

~

M OBn

OMe

20-63% ct:[3 = 3.1-6.9:1

VI.A.1-11 van der Marel, G.A. et al., OL, 5, 1947; Crich, D.; Picione, J., OL, 5, 781; see also: Durham, T.B.; Roush, W.R., OL, 5, 1871, 1875. /X"~'~,.....~OH Tf20' Ph2SO~

~o)~

T f20 ~'-(RO) n~"~'O'O~o""5~'--" L.. _ . _ . ~Y

.o-~--o I-iO-~._o 0~o~/-,,~ ss 0~o~7 ~

o / "~, 0~ ), o - ,~~7-'-.X '- o 56-87%

(RO)~

VI.A.l-12 Boebel, T.A.; Gin, D.Y., AG(E), 42, 5874. "Sulfoxide Covalent Catalysis: Application to Glycosidic Bond Formation"

USEFUL SYNTHETIC PREPARATIONS

227

VI.A.I-13 Moreau, V. et al., TL, 44, 8999 laccess to high mannose typesl; Lowary, T.L. et al., JACS, 125, 415 5 [containing r and 13-arabinofuranosyl linkages]; Whitfield, D.M. et al., JOC, 68, 2426 [lactosamine and sialylated lactosamine]; Wong, C.-H. et al., JAC, 68, 2135 [N-acetyllactosamines]. Glycosylation Routes to Oligosaccharides

VI.A.I-14 Ley, S.V. et al., OL, 5, 1147. 0 HS~ NaOMe R1

r

0

S"~

CH2CI2/MeOH L 84-94%

VI.A.I-15 Hung, S.-C. et al., JOC, 68, 8719; Ibatullin, F.M. et al., TL, 44, 7961; see also: Fuentes, J. et al., TL, 44, 6605; Schmidt, R.R. et al., JOC, 68, 5641. . r.... (AcO)n ~ r , , ,~ _ ',,~ 0 STol (HO)~',---~,~,oOH Ac20, HS-To!, Cu(OTf)2 BF3oEt2O, neat, rt 66-75% r = 0-1:1-0 [similarly with thiourea, BF3oEt20 then R-X; for azasugar thioglycoside, or for S-linked glycopeptide synthesis]

VI.A.I-16 Bettadaiah, B.K.; Srinivas, P., TL, 44, 7257; Das, S.K. et al., SL, 1607. A A

O

+ R-OH

ZnCI2

~ Ac ~ O R 60-91% tx:13= 1-3.5:1 [similarly with InCl3/btW] CH2C12, rt

VI.A.I-17 Dujardin, G. et al., TL, 44, 1491. tBu9 H

80% (other examples given)

228


VI.A.l-18 Ley, S.V. et al., OBC,1, 15. "Development of ~-Keto-l,3-dithianes as Versatile Intermediates for Organic Synthesis" VI.A.2. Acids and Anhydrides see also: I.A.2., II.B. 1, V.E VI.A.2-1 Nakata, M. et al., TA, 14, 1251. "Practical Deracemization of NM-3, A Synthetic Angiogenesis Inhibitor" VI.A.2-2 Ikunaka, M. et al., TA, 14, 1385. "A Scalable Chemoenzymatic Preparation of (R)-Tetrahydro-furan-2carboxylic Acid" VI.A.2-3 Lipton, M.A. et al., JOC,68, 7841. "Asymmetric Synthesis of Four Diastereomers of 3-Hydroxy-2,4,6trimethylheptanoic Acid: Proof of Configurational Assignment" VI.A.2-4 Wu, Z.-L.; Li, Z.-Y., Wu, Y., OBC,1,535. X---~

CC, 386 and JOC,68, 2479; Wang, M.-X.;

C~~ RhodococcusSP. 0497 cGMCC Me .~ X CN

,,.,~ ~ ~(~NH2 Me ~"~" " ~ " CO2H 31-96% ee = 97-99%

[similarly for amide to carboxylic acid transformations] VI.A.2-5 Mhaske, S.B.; Argade, N.P., S, 863; see also: Argade, N.P. et al., S, 346. o 2., H+, reflux

RO" "CO2H 90-98%

VI.A.2-6 Yoon, Y.-J. et al., S, 1517. base, THF or CI-I2CI2 R-CO2H ~,~ (R-CO2)O 02 N, N"

C~O ~ C!

48-96%

NO2


229

VI.A.2-7 Bell, A.T. et al., OL, 5, 3193. "Synthesis of Mixed Acid Anhydrides from Methane and Carbon Dioxide in Acid Solvents" VI.A.2-8 Villemin, D. et al., JCR(S), 433.

I(~ ~ R

' ' • C O 2+ HR-CHO

~tw, Ac20, NH4OAc

",~ -CO2H o 50-90%

VI.A.3. Alcohols and Related Species see also: II.B. 1, III.A, V.E, VI.A. 11 VI.A.3-1 Kishi, Y. et al., TL, 44, 7489. "Application of Chiral Bidentate NMR Solvents for Assignment of the Absolute Configuration of Alcohols: Scope and Limitation" VI.A.3-2 Anson, M.S. et al., SL, 679. "The First Supported N-Pyridinyl Proline-Derived Chiral Catalyst for the Kinetic Resolution of Racemic Alcohols" VI.A.3-3 Clapes, P. et al., JOC, 68, 5351. "Novel Chemoenzymatic Strategy for the Synthesis of Enantiomerically Pure Secondary Alcohols with Sterically Similar Substituents" VI.A.3-4 Anthonsen, T. et al., TL, 44, 8453; see also: Kroutil, W. et al., TA, 14, 275. "Enhanced Selectivity in Novozyn 435 Catalyzed Kinetic Resolution of 2 ~ Alcohols and Butanoates Caused by the (R)-Alcohols" VI.A.3-5 Miyashita, M. et al., CC, 2482. 1. BuB(OH)2, Pd(PPh3)4, Ph-Me, rt ~ C O 2

R1 2. H202, H20/MeOH, rt

OH R J,~/A ~-,,~ ",,,~ --CO2R1 OH 71-94% dr = 19-99:1

230


VI.A.3-6 Holland, H.L. et al., TA, 14, 289; Ghanem, A.; Schurig, V., TA, 14, 57; Easwar, S.; Argade, N.P., TA, 14, 333; Yuan, C. et al., TA, 14, 63. Lipase-Catalyzed Resolutions VI.A~ Stewart, I.C.; Bergman, R.G.; Toste, F.D., JACS, 125, 8696. "Phosphine-Catalyzed Hydration and Hydroalkoxylation of Activated Olefins: Use of a Strong Nucleophile to Generate a Strong Base" VI.A.3-8 Davies, S.G. et al., SL, 1659. O o

H ~ '~Ph OH

R

or LAH, THF, rt

~)n 60-99% de = 98%

VI.A.3-9 Fan, R.-H.; Hou, X.-L., OBC, 1, 1565; Gonzalez, C. et al., JOC, 68, 2248; Rao, K.R. et al,. JOC, 68, 4994. R1

R1

R~O

Bu4NHSO4 ~ _ R ~ o H20, 20-45~

H

()H

61-98% [other epoxide ring openings reported with alkoxide nucleophiles and different catalysts]

VI.A.3-10 Zhong, G., AG(E), 42, 4247. H

Ph-NO +

R^ C H O

1. proline, DMSO, rt

o,N',ph R ~ , , OH

2. NaBH, EtOH

54-86% ee = 94-99%

VI.A.3-11 Mioskowski, C. et al., TL, 44, 4451. ph~SO2Ph R

1. BuLi, Ph-Me, -78~ 2. BRla 3. H202, NaOH

rt

p h ~ ' . . ~ OH R" "g 1 53-82%


231

VI.A.3-12 Maleczka, Jr., R.E.; Smith, III, M.R. et al., JACS, 125, 7792. Z Z Y-~ ~oqB 1"Ir(Ind,Ir(c~ dmpc' neat Y - - ~ + H ~ OH 2. Oxone, H20/Me2CO, 250C X X 51-89%

VI.A.3-13 Bonin, M.; Micouin, L.; Knochel, P. et al., SL, 2240; Laschat, S. et al., SL, 2175; Fernandez, E. et al., TA, 44, 1611 and Fernandez, E. et al., CEJ, 9, 191. 1. [Ir(cod)Cl]~ CatBI-I,0*C r ~ PPh2 ~.N...CO2Bn I~"~r

Bn

~'~

HO~.N...CO2B n

2. n202, aq NaOH

~

[ " ~ r "CO2Bn

76% ee = 71% [other asymmetrichydroborations reported with different catalysts and substrates]

VI.A.4. Aldehydes and Ketones see also: I.A.1, I.G.2, II.A.1 VI.A.4-1 Suzuki, Y. et al., CC, 1314. O2N--@F

-I- Ar-CNO

Na.

r--a Me'N',~§

~9 02

r

46-77%

VI.A.4-2 Kosrnrli, J.; Weigel, L.O. et al., JACS, 125, 3208. "Unfunctionalized, tx-Epimerizable Nonracemic Ketones and Aldehydes Can Be Accessed by Crystallization-Induced Dynamic Resolution of Imines" VI.A.4-3 Davies, S.G. et al., OBC, 1,2001. "N-Acyl-5,5-Dimethyloxazolidin-2-ones as Latent Aldehyde Equivalents" VI.A.4-4 Shi, Y. et al., JOC, 68, 4963. "An Improved Synthesis of a Ketone Catalyst for Asymmetric Epoxidation of Olefins"

232


VI.A.4.5 Hidai, M. et al., JOM, 679, 32. OTMS R~R [RuCI(h2"H2)(dppe)2]OTf -I- D2 1 DCE, 50~

O

40-95%

VI.A.4-6 Rao, K.R. et al., JOC, 68, 9119; Weinreb, S.M. et al., JOC, 68, 3323. O ph..~O IBX .~ p h i . , , x H20, rt 82-92% VI.A.4-7 Uemura, S. et al., JACS, 125, 8862. R _ OH Pd(OAc)2, Cs2CO3, Ph-Me R~N)~R2~V" + R3"X

Jt

R

2

~ 27-99% ee = 22-95 %

VI.A.4-8 Wang, L. et al., TL, 44, 4685. 1. CBr4, PPh 3, CH2C12 R-CHO 2. Zn, H20, 275"C

MemO R 48-88%

VI.A.4-9 Liebeskind, L.S. et al., OL, 5, 3033" Urawa, Y.; Ogura, K., TL, 44, 271. ToI-S~O + Bu3SnR1 Pd2(dba)3, P(furyl)3, CuOP(O)Ph2~ R ~ O R

R

61-97% [similarly with arylboronic acids/acid chlorides and palladium catalysis] VI.A.4-10 Yadav, J.S. et al., SL, 1722 and S, 2390; Fukuyama, T. et al., SL, 1512. (~CI R

+ TMS u

R1

12 ~ CH2C12, rt

~\

-_.

R1

85-90% [similarly with an InBr3 catalyst or with a thioester and a terminal alkyne under Pd catalysis]


233

VI.A.4-11 LubelI, W.D. et al., OL, 5, 4887. R-CO2Me + "~MgBr

Cu(OAc)2 _ THF, -45~

O R~,,.,~ 26-77%

VI.A.5. Amides and Related Soecir _

VI.A.5-1 Grzyb, J.A.; Batey, R.A., TL, 44, 7485; Beaudoin, S. et al.,

JOC, 68, 115. O

O

IL ~ I ~ i ~ N +.Me + R2.CO2H

T E Art~ R tLN~R2 MeCN, ~1 75-99%

[similarly for sulfonamide synthesis] VI.A.5-2 Shiina, I.; Kawakita, Y., TL, 44, 1951; Giacomelli, G. et al., OL, 5, 2715; Kim, M. et al., SC, 33, 4013; Srinivas, K.V.N.S.; Das, B., JOC, 68, 1165. no base O~NR1R 2 9 R O O 82-99% [similar carboxylic acid activation/displacement with cyanuric chloride/hydroxylamine; trichloromethyl chloroformate/ N,O-dimethylhydroxylamineor with an alkyl carboxylic acid (in competition with an aryl carboxylic acid) and RNH2/Fe3+-K10clay] R-CO2H +

~N~o~

~ O"

VI.A.5-3 Khalafi-Nezhad, A. et al., TL, 44, 7325. R-CO2H + (NH2)2C=O gW, imidazole ~ O~NH2 R

47-88% VI.A.5-4 Williams, L.J. et al., JACS, 125, 7754; Fazio, F.; Wong, C.H., TL, 44, 9083; Damkaci, F.; DeShong, P., JACS, 125, 4408. ~SH n /

R

+ R1.N3

pyr-Me2 MeOH/CHCI3

H R

64-99% [similarly with RuCl3 or with a sugar azide/PPh3 and CuCI2.2H20]

234


VI.A.5-5 Wang, T. et al., OL, 5, 3399. "Selective Monoacylation of Symmetrical Diamines via Prior Complexation with Boron" VI.A.5-6 Aube, J. et al., JACS, 125, 7914. "Asymmetric Schmidt Reaction of Hydroxyalkyl Azides with Ketones" VI.A.5-7 Ballini, R. et al., T, 59, 1143. O R~ R1 + R2.NH2 NO2

O

~N.R 2 neat, rt

H 6-99%

VI.A.5-8 Kraus, G.A. et al., S, 19. O R

H2#'CO2R1 MeCN, rt ~Pr

O

R

H 30-77%

VI.A.5-9 Ishino, Y.; Komatsu, M. et al., S, 2317. KF/AI203 R.N~CHO R-NH + CHCI3 ~1 MeCN, rt ~1 67-93% VI.A.5-10 Ray, S. et al., TL, 44, 7637; Feroci, M.; Inesi, A. et al., JOC, 68, 1548. O R~OH + HN..R2 CO2,DEAD,PPh3 ~ R ~ O ~ N oR2 ~1 80-120~ ~1 80-98%

[carbamate formation also with CO2 then EtI] VI.A.5-11 Cook, G.R. et al., JACS, 125, 5115. O o o A r ~ . ~ ~ O + H-NPhth [Pd(C3H$)CI]~,BINAP,THFK-NPhth (cat)~ Ph - A r ' ~-H Vh'~r

~ ~lPhth (sulfonamides, amines and malonates add to terminal carbon) 95-99%


235

VLA.5-12 Reddy, K.L., TL, 44, 1453; Gullickson, G.C.; Lewis, D.E., S, 681" see also: Chen, J.J.; Deshpande, S.V., TL, 44, 8873. O X--~ CN MeCO2tBu~ X ~ ~A- H JL N".~Bu H2SO4,42~ 88-95 %

[similarly with diphenylmethanolor via reaction of acid chlorideswith isocyanides] VI.A.5-13 Lu, S. et al., JCR(S), 442; Chiarotto, I.; Feroci, M., JOC, 68, 7137. R___f-~

k=-r

NH2

;2~/ m

R1 Fe, CO, TEA R _ _ ~ N O H N ~ _ . ~ / ,~ R1 Ph-Me, 130*C

69-91% [symmetricalureas from RNH2,CO, Pd catalysts, electolysis] VI.A.5-14 Shie, J.-J.; Fang, J.-M., JOC, 68, 1158. 1. aq NH3,12 O.~,,,NH2 R-CHO 1 2. H202 R 81-98% VI.A.5-15 Duthaler, R.O., AG(E), 42, 975; Jorgensen, K.A. et al., AG(E), 42, 1367; Brase, S. et al., CC, 2448; see also: Kinart, W.J.; Kinart, C.M., JOM, 665, 233. R~R

N"CO2R2 CH2C12,rt O HN"CO2R2 4. ~.- R ~ C O 2 R 2 1 R202C'N ~COz[. I ll H

67-92% ee = 79-99%

VI.A.5-16 Xia, C.-G. et al., SL, 2337 and CC, 2570; see also: Jung, Y.H. et al., JOC, 68, 3721. O R202C~NH O R ~ R

1

+ R202C NH2

TBAB, BF3oEt20 R .~. rt

[similar SN2'reactions reported]

~

R

29-50%

1

236


VI.A.5-17 Kalbalka, G.W." Guchhait, S.K., OL, 5, 4129. H CuCI, 3/k MS R tBuO2C.N,,NH2 + R-B(OH)2 pyr/DCE,rt ,I~ tBuO2C.N,~s,,CO2tBu H 63-87% VI.A.5-18 Wu, Z.-L.; Li, Z.-Y., TA, 14, 2133; Wang, M.-X. et al., JOC, 68, 4570; Sharghi, H." Sarvari, M.H., SC, 33, 207.

ho ococcuss,

CN

CGMCC0497

~

' ~ "ff-NH2 O 20-92% ee = 2-81% [non-enzymatic nitrile to amide conversionreported with MSA/AI203] VI.A.5-19 Buchwald, S.L. et al., JACS, 125, 6653. "Expanding Pal-Catalyzed C--N Bond-Forming Processes: The First Amidation of Aryl Sulfonates, Aqueous Amination and Complementarity with Cu-Catalyzed Reactions" VI.A.5-20 Ghosh, A. et al., OL, 5, 2207; Wallace, D.J. et al., OL, 5, 4749. R R1 R2 R1 R2 ~,Cl "I" a % ~ o' ( Pd2(dba)3'Cs2CO3'Ph'Me'100~ .~" ~ ~ o ~ O o

x [similar coupling with amides and vinyl triflates]

11-99%

VI.A.5-21 Wannberg, J.; Lathed, M., JOC, 68, 5750. R-~~'~,IX +

H'NR1R2

O tIW, Mo(CO)6,Pd(OAc)2,DBU - Rr ~ ~ N R I R 2 _ ~ " THF, 100 or 1500C,air 35-95%

VI.A.5-22 Cunico, R.F.; Maity, B.C., OL, 5, 4947. %NMe2 X Pd(PPh3)4 O_~_NMe2 TMS

Ph-Me, 110~ 25-92%


237

VI.A.5-23 Terauchi, J.; Curran, D.P., TA, 14, 587; Taguchi, T. et al., JOC, 68, 9851; see also: Hsung, R.P. et al., JACS, 125, 2368.

u

Ph-Me, -40~

u 2%97%

VI.A.5-24 Overman, L.E. et al., OL, 5, 1809. MeO.,(~ MeO.,f~ R CH2C12,23~ ~ ~'-~_ 2 O p~ (Pr

p~co

R

~ N ~ F3C

O

ee = 82-94%

pl~_~Ph ~Ph

(also with Z-isomers)

VI.A.6. Amines

VI.A.6-1 Wolf, C. et al., JOC, 68, 3287. "A Convenient Method for the Determination of the Absolute Configuration of Chiral Amines" VI.A.6-2 Selva, M. et al., JOC, 68, 7374; Selva, M.; Tundo, P., TL, 44, 8149; Shieh, W.-C. et al., TL, 44, 4563; Kopach, M.E. et al., JOC, 44, 5739; Murty, M.S.R. et al., SC, 33, 2483. Na exchanged Y Faujasite Ph-NH2 + (MeO)2C=O ~ Ph-NHMe 90.150~ 77-92% [alkylations of 2~amines reported with (BnO)2CO, DABCO; benzylic chlorides or Zn/RBr] VI.A.6-3 Flynn, D.L.; Hanson, P.R. et al., TL, 44, 7187. O

1. R-OH, PPh3, DIAD, CH2CL2, reflux 2. PhCH=Ru(IMesH2)(PCy3)CI2, CH2C12 3. EtOCH=CH2 4. MeOH, filter 5. NH2NH2, THF, reflx

R-NH 2 41-90%

238


VI.A.6-4 Shibasaki, M. et al., JACS, 125, 16178; Li, K.; Hii, K.K., CC, 1132; Fustero, S.; Volonterio, A. et al., AG(E), 42, 2060; Adapa, S.R. et al., SL, 720; Srivastava, N.; Banik, B.K., JOC, 68, 2109; Xia, C.-G. et al., SL, 2425; Wabnitz, T.C.; Spencer, J.B., OL, 5, 2141; Naidu, B.N. et al., JOC, 68, 10098. o

(S)-YLB, drierite

R ~ ' , . . . ~ R 1 + NH2OMe

THF, -200C

O H31"OMe ~

R~,~R1

57-07% ee = 81-96%

[Michael aminations reported also with a dicationic BINAP Pd(II) complex; chiral amino acid derivatives/I)ABCO; Bi(OTf)3; Bi(NO3)3; copper salt or Tf2NH] VI.A.6-5 Buchwald, S.L. et al., JOC, 68, 9563. R~,~ + H.NR1R2 Pd(OAc)2or Pd2(dba)3,tBuONa ~" R--~~L~NRIR 2 ONf Ph-Me, ll0~ 59-97% VI.A.6-6 Zim, D.; Buchwald, S.L., OL, 5, 2413; Verkade, J.G. et al., JOC, 68, 452, 8416; Singer, R.A. et al., S, 1727; Maes, B.U.W. et al., SL, 1822; Cho, C.-G. et al., OL, 5, 979; Hartwig, J.F. et al., JOC, 68, 2861; Prashad, M. et al., JOC, 68, 1163; Liu, Y.; Prashad, M. et al., JHC, 40, 713; Gueiffier, A. et al., JOC, 68, 4367; Takamura-Enya, T. et al., TL, 44, 5969; Liu, Z.; Larock, R.C.; OL, 5, 4673; Ji, J. et al., OL, 5, 4611; Queiroz, M.-J.R.P. et al., T, 59, 975. R--~~,~ + H-NR1R2 tBuONa'Ph-Me'A ~ R - - ~ ~ , ~ CI ~ NR1R2 V~2 75-98% PdOAc

[various leaving groups, substrates and catalysts used for related reactions] VI.A.6-7 Kadyrov, R.; Riermeier, T.H., AG(E), 42, 5472; Bhattacharyya, S. et al., S, 2206; E1Kaim, L. et al., JOC, 68, 8733; Basu, B. et al., SL, 555. NH4HCO~ RuCI2(ToI-BINAP)~ R,,~NH 2 T. ~R10 NH3/MeOH, 85~ R1 44-93% ee = 24-95 % [reductive aminations reported also with substituted amines and other catalysts and reducing agents]


239

VI.A.6-8 Ma, D. et al., OL, 5, 2453; Twieg, R.J. et al., TL, 44, 6289; Kwong, F.Y.; Buchwald, S.L., OL, 5, 793; Fukuyama, T. et al., OL, 5, 4987; see also: Chaudhari, R.V. et al., CC, 2460. y__~ + H-NRR1 CuI, K2COa,proline ~, y _ _ ~ X

DMSO, 40-70~

NRR1 46-91%

[other Cu catalyzed aryl coupling reactions reported with different substrates] VI.A.6-9 Quach, T.D.; Batey, R.A., OL, 5, 4397; Lam, P.Y.S. et al., TL, 44, 1691; Yudin, A.K. et al., JOC, 68, 2045. R--~

+ H-NR1R2 Cu(OAc)2~ BXn

CH2CI2'4~ MS' rt ~ R - ~

02, rt-40*C

NR1R2 40-93% [aziridation of arylboronic acids reported under similar conditions] VI.A.6-10 Guo, Z.-R. et al., SL, 564; Tu, Y.-Q. et al., OL, 5, 3515; Toma, S. et al., M, 134, 37; Singaram, B. et al., OL, 5, 3867.

(:~ r ~ 0 2 X

,w,~,~2c03

+ R-NH2

ff~N~ ~ N

"R

H 60-93% [similarly with tBuOK; K2COa/ultrasound or 2-fluoropyridine/LiH3BHR2]

VI.A.6-11 Fujita, K.; Yamaguchi, R. et al., TL, 44, 2687, R1

NH2

Ph-Me, 110"C

R2 H

63-95% VI.A.6-12 Laval, G.; Golding, B.T., SL, 542. CO2H 1. NBS,DMF, phosphate buffer (pH 5) NH2 H 2. NaBH4,NiCI2.6H20, rt

R~NH2 59-81%

VI.A.6-13 Yasuda, M.; Yamashita, T. et al., JOC, 68, 7618. NH3, Et4NBF4Ar-H/Ph-CI2,Ar-H, Ph-CI2~NH2 Ar,~Ar ,, Ar~~.J,~A r MeCN/H20 71-90%

240


VI.A.6-14 Yoshida, Y. et al., SL, 2139. H

OEt

+

X

J.-

2. BH3oTHF

X 65-89%

VI.A.6-15 Hartwig, J.F. et al., JACS, 125, 5608; Belier, M. et al., JACS, 125, 10311. R~,~/ [Rh(cod)(DPEphos)]BF4R ~ + H-NR1R2 Ph-Me, 700C NRIR2 41-79% VI.A.6-16 Belier, M. et al., OL, 5, 4767; Schafer, L.L. et al., CC, 2462. 1. Ph-Me, 100*C,Me-f(

R~

~--O--Ti(NMe2)2 tBu HN-R1 + R1-NH2 ~ R---( 2. NaCNBH3,ZnCl2, MeOH, rt Me 69-99%

VI.A.6-17 Smulik, J.A.; Vedejs, E., OL, 5, 4187. MeO~~ ~ W G

EWG

tBuOK

-O-NH2 +

NH2

THF, -78~

64-67%

OMe VI.A.6-18 Hancock, M.T.; Pinhas, A.R., TL, 44, 7125. _N-Bn

Me4

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Palladium In Organic Synthesis

Microwaves in organic synthesis

Organic Synthesis

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