Science of Synthesis: Knowledge Updates 2011/2 1
Title page 5
Imprint 7
Preface 8
Abstracts 10
Overview 14
Table of Contents 16
Volume 3: Compounds of Groups 12 and 11 (Zn, Cd, Hg, Cu, Ag, Au) 32
3.6 Product Class 6: Organometallic Complexes of Gold 32
3.6.11 Organometallic Complexes of Gold (Update 1) 32
3.6.11.1 Gold-Catalyzed Cycloisomerizations of Enynes 32
3.6.11.1.1 Method 1: Cycloisomerization of 1,6-Enynes 34
3.6.11.1.1.1 Variation 1: Formation of 1,3-Dienes 34
3.6.11.1.1.2 Variation 2: Formation of Cyclobutenes or Cyclobutanones 39
3.6.11.1.1.3 Variation 3: Formation of Cyclopropyl Rings 41
3.6.11.1.1.4 Variation 4: Formation of Fused Rings by Cycloisomerization of Substituted 1,6-Enynes by Friedel–Crafts-Type Processes 43
3.6.11.1.2 Method 2: Cycloisomerization of Dienynes 46
3.6.11.1.3 Method 3: Cycloisomerization of Oxo-1,6-enynes 49
3.6.11.1.3.1 Variation 1: Applications of the Cycloisomerization of Oxo-1,6-enynes in Total Synthesis 53
3.6.11.1.4 Method 4: Inter- and Intramolecular Addition of Nucleophiles to 1,6-Enynes 55
3.6.11.1.5 Method 5: Cycloisomerization of 1,5-Enynes 64
3.6.11.1.6 Method 6: Inter- and Intramolecular Addition of Nucleophiles to 1,5-Enynes 76
3.6.11.1.7 Method 7: Cycloisomerization of 1,n-Enynes via Migration of Propargyl Groups 80
3.6.11.1.8 Method 8: Cycloisomerization of 1,7- and Higher Enynes 90
3.6.12 Organometallic Complexes of Gold (Update 2) 102
3.6.12.1 Gold-Catalyzed Propargylic Rearrangements 102
3.6.12.1.1 Synthetic Method Development Based on Gold-Catalyzed 3,3-Rearrangements of Propargylic Carboxylates 102
3.6.12.1.1.1 Reactions via Gold-Containing Oxocarbenium Intermediates 106
3.6.12.1.1.1.1 Method 1: Reactions Using Indole-3-acetyl as the Acyl Group 107
3.6.12.1.1.1.2 Method 2: Reactions of Substrates with Functionality at the Alkyne Terminus of the Propargylic Group 109
3.6.12.1.1.1.2.1 Variation 1: Using Enyne Substrates 110
3.6.12.1.1.1.2.2 Variation 2: Using 4-(Trimethylsilyl)but-2-ynyl Substrates 112
3.6.12.1.1.1.3 Method 3: Reactions of 1-Arylpropargylic Carboxylates 112
3.6.12.1.1.1.4 Method 4: Reactions with Hydrolytic Treatment 113
3.6.12.1.1.1.4.1 Variation 1: Formation of a-Unsubstituted Enones 113
3.6.12.1.1.1.4.2 Variation 2: Formation of a-Iodo- or a-Bromoenones 114
3.6.12.1.1.1.5 Method 5: Intramolecular Acyl Migration 115
3.6.12.1.1.1.6 Method 6: Reactions Incorporating Gold(I)/Gold(III) Catalysis 117
3.6.12.1.1.1.6.1 Variation 1: Gold-Catalyzed Oxidative Homocoupling 117
3.6.12.1.1.1.6.2 Variation 2: Gold-Catalyzed Oxidative Cross-Coupling Reaction 118
3.6.12.1.1.1.6.3 Variation 3: Gold-Catalyzed Oxidative C--O Bond Formation 119
3.6.12.1.1.2 Nucleophilic Attack on the (Acyloxy)allene at the ß- or .-Position 121
3.6.12.1.1.2.1 Method 1: Nucleophilic Attack at the .-Position 122
3.6.12.1.1.2.2 Method 2: Nucleophilic Attack at the ß-Position 125
3.6.12.1.1.3 (Acyloxy)allenes as Nucleophiles 126
3.6.12.1.1.4 (Acyloxy)allenes as All-Carbon 1,3-Dipoles 129
3.6.13 Organometallic Complexes of Gold (Update 3) 132
3.6.13.1 Gold-Catalyzed Coupling Reactions 132
3.6.13.1.1 Oxidative Coupling with Gold(III) as a Stoichiometric Oxidant 132
3.6.13.1.1.1 Method 1: Reductive Elimination from Stoichiometric Organogold(III) Complexes 132
3.6.13.1.1.2 Method 2: Oxidative Chlorination of Nonactivated Arenes 133
3.6.13.1.1.3 Method 3: Oxidative Alkynylation of Nonactivated Arenes 134
3.6.13.1.1.4 Method 4: Oxidative Amination of Nonactivated Arenes 135
3.6.13.1.1.5 Method 5: Oxidative Homocoupling via C--H Bond Functionalization 135
3.6.13.1.1.6 Method 6: Homocoupling as a Side Reaction in Cyclizations Catalyzed by Gold(III) 137
3.6.13.1.2 Gold-Catalyzed Cross Coupling with Substrates as Oxidants 139
3.6.13.1.2.1 Method 1: Gold-Catalyzed Suzuki Reactions 139
3.6.13.1.2.2 Method 2: Gold-Catalyzed Sonogashira Reactions 140
3.6.13.1.2.3 Method 3: Gold-Catalyzed Alkynylation of Heterocycles Using Alkynyliodine(III) Reagents 142
3.6.13.1.3 Gold-Catalyzed Oxidative Homocoupling with External Oxidants 146
3.6.13.1.3.1 Method 1: Homocoupling of Nonactivated Arenes Using (Diacetoxyiodo)benzene 147
3.6.13.1.3.2 Method 2: Synthesis of Dicoumarins via Cyclization–Homocoupling Using tert-Butyl Hydroperoxide 148
3.6.13.1.3.3 Method 3: Cyclization–Homocoupling of 2-Alkynylphenols with (Diacetoxyiodo)benzene 149
3.6.13.1.3.4 Method 4: Homocoupling of Propargyl Acetates Using Selectfluor 150
3.6.13.1.3.5 Method 5: Homocoupling from Stoichiometric Organogold(I) Complexes Using Electrophilic Fluorinating Reagents 152
3.6.13.1.4 Gold-Catalyzed Oxidative Cross Coupling with External Oxidants 153
3.6.13.1.4.1 Method 1: Oxidative Alkynylation of Nonactivated Arenes Using (Diacetoxyiodo)benzene 153
3.6.13.1.4.2 Method 2: Oxidative Diamination of Alkenes Using (Diacetoxyiodo)benzene 155
3.6.13.1.4.3 Method 3: Synthesis of 1-Carboxyvinyl Ketones via Oxidative C--O Bond Formation Using Selectfluor 157
3.6.13.1.4.4 Method 4: Oxidative Arylation with Arylboronic Acids Using Selectfluor 159
3.6.13.1.4.4.1 Variation 1: Synthesis of a-Aryl Enones from Propargyl Acetates 159
3.6.13.1.4.4.2 Variation 2: Oxidative Carboheterofunctionalization of Alkenes 161
3.6.13.1.4.4.3 Variation 3: Synthesis of a-Aryl a-Fluoro Ketones via Oxidative Functionalization of Alkynes 165
3.6.13.1.4.5 Method 5: Oxidative Arylation with Arylsilanes Using Selectfluor 166
3.6.13.1.4.6 Method 6: Oxidative Aminooxygenation and Aminoamidation of Alkenes Using Selectfluor or (Diacetoxyiodo)benzene 167
3.6.13.1.4.7 Method 7: Cascade Cyclization–Intramolecular Arylation with Nonactivated Arenes Using External Oxidants 171
3.6.13.1.4.7.1 Variation 1: Cascade Cyclization–Intramolecular Arylation of Benzyl-Substituted Allenoates Using Selectfluor 171
3.6.13.1.4.7.2 Variation 2: Cascade Cyclization–Intramolecular Arylation of Alkenes 175
3.6.13.1.4.8 Method 8: Cascade Cyclization–Oxidative Alkynylation of Allenoates Using Selectfluor 178
3.6.13.1.4.9 Method 9: Isolation of a Gold(III) Fluoride Complex and Its Use in Cross Coupling 180
Volume 5: Compounds of Group 14 (Ge, Sn, Pb) 184
5.2 Product Class 2: Tin Compounds 184
5.2.27 Product Subclass 27: Benzylstannanes 184
Synthesis of Product Subclass 27 184
5.2.27.1 Method 1: Synthesis from (Trialkylstannyl)- or (Triarylstannyl)lithiums 184
5.2.27.1.1 Variation 1: From (Trialkylstannyl)- or (Triarylstannyl)lithiums and Benzyl Halides 184
5.2.27.1.2 Variation 2: From (Trialkylstannyl)lithiums or (Trialkylstannyl)sodiums and a,ß-Unsaturated Esters 185
5.2.27.2 Method 2: Synthesis from Organomagnesium Derivatives and Organotin Halides 186
5.2.27.2.1 Variation 1: From Benzyl Halides by Barbier Reactions 186
5.2.27.2.2 Variation 2: Sonication-Promoted Barbier Reactions 187
5.2.27.2.3 Variation 3: From Benzyl Halides by Grignard Reactions 188
5.2.27.3 Method 3: Synthesis from Benzyllithiums and Stannyl Halides 189
5.2.27.3.1 Variation 1: From Benzyllithiums without Directing Groups 189
5.2.27.3.2 Variation 2: From Benzyllithiums with Directing Groups 191
5.2.27.3.3 Variation 3: From Benzyllithiums Prepared by Carbolithiation 192
5.2.27.3.4 Variation 4: From Diastereomerically Enriched Benzyllithiums Containing a Rotationally Restricted Amide 193
5.2.27.3.5 Variation 5: From Diastereomerically Enriched Benzyllithiums Prepared from Enantioenriched Sulfoxides 194
5.2.27.3.6 Variation 6: From Enantiomerically Enriched Benzyllithiums Prepared by Enantioselective Deprotonation 195
5.2.27.4 Method 4: Synthesis from Benzylzincs and Stannyl Halides 197
5.2.27.4.1 Variation 1: From Benzyl Halides by Barbier Reactions 197
5.2.27.4.2 Variation 2: From Benzylzincs via Transmetalation to Benzylcuprates 198
5.2.27.5 Method 5: Synthesis from Arylzincs and (Iodomethyl)stannanes 200
5.2.27.6 Method 6: Synthesis from Stannyl Anion Equivalents and Carbonyl Derivatives 201
5.2.27.6.1 Variation 1: Addition of Stannyllithiums to Aldehydes 201
5.2.27.6.2 Variation 2: Addition of Tributyl(trimethylsilyl)stannane to Aldehydes 201
5.2.27.6.3 Variation 3: Addition of Stannyllithiums or Stannylzincs to Enantiomerically Enriched N-Sulfinylimines 202
5.2.27.7 Method 7: Palladium-Catalyzed Insertion of Benzyl Halides into Hexaalkyldistannanes 204
5.2.27.8 Method 8: Synthesis by Silicon–Tin Transmetalation 205
5.2.27.9 Method 9: Hydrostannylation of Alkenes 205
5.2.27.9.1 Variation 1: Radical Hydrostannylation of Alkenes 205
5.2.27.9.2 Variation 2: Palladium-Catalyzed Hydrostannylation of Alkenes 206
5.2.27.10 Method 10: Palladium-Catalyzed Distannylation of o-Quinodimethanes 207
5.2.27.11 Method 11: Synthesis by Sommelet–Hauser Rearrangement of Tetraalkylammonium Salts 208
Applications of Product Subclass 27 in Organic Synthesis 210
5.2.27.12 Method 12: Transmetalation 210
5.2.27.12.1 Variation 1: Transmetalation To Afford Alkali Metal Derivatives 210
5.2.27.12.2 Variation 2: Transmetalation To Afford Other Metal Derivatives 212
5.2.27.13 Method 13: Stille Couplings 212
5.2.27.13.1 Variation 1: Coupling to Aryl Bromides 212
5.2.27.13.2 Variation 2: Coupling to Vinyl Trifluoromethanesulfonates 213
5.2.27.13.3 Variation 3: Coupling to Acyl Chlorides 214
5.2.27.14 Method 14: Palladium-Free Coupling to a-Oxo Acid Chlorides 215
5.2.27.15 Method 15: Nucleophilic Addition to N-(Alkoxycarbonyl)pyridinium Salts 215
5.2.27.16 Method 16: Three-Component Coupling of Imines, Acid Chlorides, and Benzylstannanes 216
5.2.28 Product Subclass 28: Allylstannanes 220
Synthesis of Product Subclass 28 220
5.2.28.1 Method 1: Synthesis from Allylmagnesium Reagents and Stannyl Halides 220
5.2.28.1.1 Variation 1: Via Preformed Allyl Grignards 221
5.2.28.1.2 Variation 2: Via Barbier Reaction 222
5.2.28.1.3 Variation 3: Sonication-Promoted Barbier Reactions 223
5.2.28.1.4 Variation 4: Sonication-Promoted Barbier Reactions with Hexabutyldistannoxane 224
5.2.28.2 Method 2: Synthesis from Allyllithium Derivatives and Stannyl Halides 225
5.2.28.2.1 Variation 1: Via Alkene Deprotonation 225
5.2.28.2.2 Variation 2: Via Lithium–Halogen Exchange 227
5.2.28.2.3 Variation 3: From Allyl Thioethers 228
5.2.28.2.4 Variation 4: From Enantiomerically Enriched Allyllithiums Prepared by Enantioselective Deprotonation 229
5.2.28.3 Method 3: Synthesis from Allylzincs and Stannyl Halides 230
5.2.28.4 Method 4: Synthesis by Silicon–Tin Transmetalation 232
5.2.28.5 Method 5: Synthesis from Stannyl Anion Equivalents and Allylic Halides, Sulfides, and Methanesulfonates 233
5.2.28.5.1 Variation 1: Via Stannyllithiums 233
5.2.28.5.2 Variation 2: Via Stannylcopper Compounds 236
5.2.28.5.3 Variation 3: Via Stannylpalladium Species 238
5.2.28.6 Method 6: Synthesis from Allylic Acetates, Benzoates, and Phosphates 238
5.2.28.6.1 Variation 1: Palladium-Catalyzed Reaction of Diethyl(tributylstannyl)aluminum and Allylic Acetates 238
5.2.28.6.2 Variation 2: Palladium-Catalyzed Reaction of Diethyl(tributylstannyl)aluminum and Allylic Phosphates 239
5.2.28.6.3 Variation 3: Palladium-Catalyzed Reduction of Allylic Acetates 241
5.2.28.6.4 Variation 4: Copper-Catalyzed Reaction of Bis(tributylstannyl)zinc and Allylic Benzoates 241
5.2.28.6.5 Variation 5: Palladium-Catalyzed Reaction between Samarium(II) Iodide, Stannyl Halides, and Allylic Acetates 243
5.2.28.7 Method 7: Synthesis from Allylic Sulfur Derivatives 244
5.2.28.7.1 Variation 1: Via Sulfides 244
5.2.28.7.2 Variation 2: Via Allylic Sulfones 245
5.2.28.7.3 Variation 3: Via Allylic S-Substituted S-Methyl Dithiocarbonates 248
5.2.28.8 Method 8: Synthesis via Wittig Reaction 250
5.2.28.9 Method 9: Synthesis of a-Substituted Allylstannanes by Selenoxide Elimination 252
5.2.28.10 Method 10: Synthesis from Stannyl Anion Equivalents and a,ß-Unsaturated Carbonyl Derivatives 253
5.2.28.10.1 Variation 1: 1,2-Addition to a,ß-Unsaturated Aldehydes and Ketones 253
5.2.28.10.2 Variation 2: 1,4-Addition to a,ß-Unsaturated Ketones Followed by Enamine Formation 255
5.2.28.10.3 Variation 3: Via ß-Stannyl Enolate Esters Prepared by 1,4-Addition to a,ß-Unsaturated Esters 257
5.2.28.11 Method 11: Synthesis from Allenes 259
5.2.28.11.1 Variation 1: Via Stannylcupration of Allenes 259
5.2.28.11.2 Variation 2: Palladium-Catalyzed Addition of Distannanes and Silastannanes to Allenes 261
5.2.28.11.3 Variation 3: Hydrostannylation of Allenes 263
5.2.28.11.4 Variation 4: Palladium-Catalyzed Acylstannylation of Allenes 265
5.2.28.11.5 Variation 5: Palladium-Catalyzed Distannylation of In Situ Generated Allenes 266
5.2.28.12 Method 12: Synthesis from Vinylstannanes 266
5.2.28.12.1 Variation 1: From Vinylstannanes and Ethene 266
5.2.28.12.2 Variation 2: Via Lewis Acid Catalyzed Addition of Alkylcuprates to Vinylstannane Acetals 267
5.2.28.13 Method 13: Synthesis from 1,3-Dienes 269
5.2.28.13.1 Variation 1: Platinum-Catalyzed Silylstannylation of 1,3-Dienes 269
5.2.28.13.2 Variation 2: Nickel-Catalyzed Acylstannylation of 1,3-Dienes 269
5.2.28.14 Method 14: Synthesis from Allylstannanes 270
5.2.28.14.1 Variation 1: Addition of Organometallic Species to Allylstannyl Halides 270
5.2.28.14.2 Variation 2: Rearrangement of Allylstannanes 271
5.2.28.15 Method 15: Synthesis by the Hydrolysis of Borylallylic Stannanes 272
5.2.28.16 Method 16: Additional Methods 272
Applications of Product Subclass 28 in Organic Synthesis 274
5.2.28.17 Method 17: Radical Reactions 274
5.2.28.18 Method 18: Cross-Coupling Reactions 278
5.2.28.19 Method 19: Transmetalations 279
5.2.28.20 Method 20: Reactions with Aldehydes, Ketones, and Their Derivatives 281
5.2.28.21 Method 21: Catalytic Enantioselective Addition to Aldehydes 285
5.2.28.22 Method 22: Nucleophilic Addition to N-Acyliminium Ions 287
Volume 9: Fully Unsaturated Small Ring Heterocycles and Monocyclic Five-Membered Hetarenes with One Heteroatom 292
9.9 Product Class 9: Furans 292
9.9.5 Furans 292
9.9.5.1 Synthesis by Ring-Closure Reactions 294
9.9.5.1.1 By Formation of One O--C and One C--C Bond 294
9.9.5.1.1.1 Fragments O--C--C and C--C 294
9.9.5.1.1.1.1 From a-Heterofunctionalized Ketones or Aldehydes 294
9.9.5.1.1.1.1.1 Method 1: From a-Halo Ketones and 1,3-Dicarbonyl Compounds (Feist-Benary Reaction) 294
9.9.5.1.1.1.1.2 Method 2: Rhodium-Catalyzed Reaction of a-Diazocarbonyl Compounds with Alkynes 295
9.9.5.1.1.1.1.3 Method 3: From a-Oxy Ketones or Aldehydes and Dicarbonyl Compounds 296
9.9.5.1.1.1.1.4 Method 4: From a-Oxyaldehydes and Enones 296
9.9.5.1.1.1.2 From 1,3-Dicarbonyl Compounds 297
9.9.5.1.1.1.2.1 Method 1: From 1,3-Dicarbonyl Compounds and Aldose Sugars 297
9.9.5.1.1.1.2.2 Method 2: From 1,3-Dicarbonyl Compounds and Propargyl Alcohols 299
9.9.5.1.1.1.2.3 Method 3: From 1,3-Dicarbonyl Compounds and But-2-ene-1,4-diones 300
9.9.5.1.1.1.2.4 Method 4: From 1,3-Dicarbonyl Compounds and 1,4-Diphenylbut-2-yne-1,4-dione 300
9.9.5.1.1.1.2.5 Method 5: From 1,3-Dicarbonyl Compounds and Bromoallenes 301
9.9.5.1.1.1.2.6 Method 6: From 1,3-Dicarbonyl Compounds and Nitroalkenes 301
9.9.5.1.1.1.2.7 Method 7: From 1,3-Dicarbonyl Compounds and Alkynoates 302
9.9.5.1.1.1.3 From Functionalized Alkenes and Alkynes with C--C--O Building Blocks 303
9.9.5.1.1.1.3.1 Method 1: From Diethyl Acetylenedicarboxylate and Propargyl Alcohols 303
9.9.5.1.1.1.3.2 Method 2: From Dimethyl Acetylenedicarboxylate, Aldehydes, and Thiazolium Salts 303
9.9.5.1.1.2 Fragments C--C--C and O--C 304
9.9.5.1.1.2.1 Method 1: Cyclization between 2,3-Bis(trimethylsilyl)buta-1,3-diene and Acyl Chlorides 304
9.9.5.1.1.2.2 Method 2: From Ketene S,S-Acetals and Aldehydes 305
9.9.5.1.1.2.3 Method 3: Reaction between Isocyanides, Dialkyl Acetylenedicarboxylates, and 1-Aryl-2-(arylamino)-2-hydroxyethanones 306
9.9.5.1.1.2.4 Method 4: Cyclization between Propargylic Dithioacetals and Aldehydes 307
9.9.5.1.1.3 Fragments O--C--C--C and C 308
9.9.5.1.1.3.1 Method 1: From Terminal Ynones and Aldehydes 308
9.9.5.1.1.3.2 Method 2: From Enones, Aldehydes, and Isocyanides 309
9.9.5.1.1.3.3 Method 3: From 1,3-Dicarbonyl Compounds and Cyclohexyl Isocyanide 310
9.9.5.1.1.3.4 Method 4: From a,ß-Unsaturated Carbonyl Compounds and Chromium Carbenes 310
9.9.5.1.1.3.5 Method 5: From Alkynyl Ketones and Diazoacetates 311
9.9.5.1.1.3.6 Method 6: Rhodium-Catalyzed Hydroformylation of Propargyl Alcohols 312
9.9.5.1.1.3.7 Method 7: From Dialkyl Acetylenedicarboxylates, Isocyanides, and Carbonyl Compounds 312
9.9.5.1.2 By Formation of Two C--C Bonds 314
9.9.5.1.2.1 Fragments C--O--C and C--C 314
9.9.5.1.2.1.1 Method 1: Condensation of Dimethyl Diglycolate with Aryl(oxo)acetates 314
9.9.5.1.2.1.2 Method 2: Reaction of Carbonyl Ylides and Alkynes 315
9.9.5.1.3 By Formation of One O--C Bond 315
9.9.5.1.3.1 Fragment O--C--C--C--C 315
9.9.5.1.3.1.1 By Cyclization of 1,4-Diheterofunctional C4 Compounds 315
9.9.5.1.3.1.1.1 Method 1: 1,4-Diazabicyclo[2.2.2]octane-Catalyzed Reaction of a-Halo Carbonyl Compounds with Dimethyl Acetylenedicarboxylate 316
9.9.5.1.3.1.1.2 Method 2: Reactions Involving N-Heterocyclic Carbenes, Activated Alkynes, and Aldehydes 316
9.9.5.1.3.1.1.3 Method 3: Cyclization of 1,4-Dicarbonyl Compounds 317
9.9.5.1.3.1.1.4 Method 4: Cyclization of .-Ketoamides 318
9.9.5.1.3.1.1.5 Method 5: Cyclization of 4-Hydroxybut-2-enals and 4-Hydroxybut-2-enones 319
9.9.5.1.3.1.1.6 Method 6: Cyclization of But-2-ene-1,4-diones 320
9.9.5.1.3.1.1.7 Method 7: Cyclization of Alk-2-yne-1,4-diols 321
9.9.5.1.3.1.1.8 Method 8: From Alkenyl Aryl Ketones and Dichloromethyl Phenyl Sulfoxide 322
9.9.5.1.3.1.1.9 Method 9: From Baylis–Hillman Adducts of Alkyl Vinyl Ketones 323
9.9.5.1.3.1.1.10 Method 10: From .,d-Epoxyacrylates 324
9.9.5.1.3.1.2 By Cyclization of Monofunctionalized C4 Compounds 325
9.9.5.1.3.1.2.1 Method 1: Cyclization of (Z)-2-En-4-yn-1-ols 325
9.9.5.1.3.1.2.2 Method 2: Cyclization of 2-En-4-yn-1-ones 326
9.9.5.1.3.1.2.3 Method 3: Cyclization of Pent-4-ynones 328
9.9.5.1.3.1.2.4 Method 4: Cyclization of But-3-yn-1-ols and 2-Alkynylcycloalk-2-enols 330
9.9.5.1.3.1.2.5 Method 5: Cyclization of But-3-yn-1-ones 331
9.9.5.1.3.1.2.6 Method 6: Cyclization of 2-(Alk-1-ynyl)alk-2-en-1-ones 332
9.9.5.1.3.1.2.7 Method 7: Cyclization of Allenols 334
9.9.5.1.3.1.2.8 Method 8: Cyclization of Allenones 336
9.9.5.1.3.1.2.9 Method 9: Cyclization of Alk-3-yne-1,2-diols 342
9.9.5.1.3.1.2.10 Method 10: Electrophilic Cyclization of Propargylic Oxirane Derivatives 344
9.9.5.1.3.1.2.11 Method 11: Cyclization of 1-Alkynyl-2,3-epoxy Alcohols 345
9.9.5.1.3.1.2.12 Method 12: Electrophilic Cyclization of 1-(Alk-1-ynyl)cyclopropyl Ketones 346
9.9.5.1.3.1.2.13 Method 13: Cyclization of Cyclopropylidene and Cyclopropenyl Ketones 347
9.9.5.1.3.1.2.14 Method 14: Wacker-Type Oxidative Cyclization of Alkenones 349
9.9.5.1.3.1.2.15 Method 15: Cyclization of 1,3-Dienyl Ethers or 1,3-Dien-1-ols 349
9.9.5.1.3.1.2.16 Method 16: Michael-Type Cyclization of 2,4-Unsaturated 1,6-Dicarbonyl Systems 351
9.9.5.1.3.1.2.17 Method 17: Methylsulfanylation of .-Disulfanyl Carbonyl Compounds 351
9.9.5.1.3.1.2.18 Method 18: Electrophilic Cyclization of 4-Sulfanylbut-2-yn-1-ols via [1,2]-Migration of the Sulfanyl Group 352
9.9.5.1.3.1.2.19 Method 19: Cycloisomerization of a-Sulfanyl Allenes 353
9.9.5.1.3.1.2.20 Method 20: Cyclization of Acetylene–Cobalt Complexes with (Vinyloxy)silanes 354
9.9.5.1.4 By Formation of One C--C Bond 354
9.9.5.1.4.1 Fragment C--O--C--C--C 354
9.9.5.1.4.1.1 Method 1: Cyclization of (2-Cyanovinyloxy)malonates 354
9.9.5.1.4.1.2 Method 2: Ring-Closing Metathesis of Homoallylic Enol Ethers 355
9.9.5.1.4.2 Fragment C--C--O--C--C 355
9.9.5.1.4.2.1 Method 1: Intramolecular Michael-Type Addition of a 3-Oxa-1,5-enyne 355
9.9.5.1.4.2.2 Method 2: Cyclization of 2'-Bromoallylic Propargyl Ethers 356
9.9.5.1.4.2.3 Method 3: Palladium-Catalyzed Cycloisomerization of Allyl Propargyl Ethers 356
9.9.5.1.4.2.4 Method 4: Reductive Cyclization of Propargyl 2,2,2-Trichloroethyl Ethers 357
9.9.5.1.4.2.5 Method 5: Radical Cyclization of Divinyl Ethers 357
9.9.5.1.4.2.6 Method 6: Ring-Closing Metathesis of Diallylic Ethers 358
9.9.5.2 Synthesis by Ring Transformation 359
9.9.5.2.1 Ring Enlargement 359
9.9.5.2.1.1 Method 1: Ring-Opening Cycloisomerization of Methylene- or Alkylidenecyclopropyl Ketones 360
9.9.5.2.2 From Five-Membered Heterocycles 361
9.9.5.2.2.1 Method 1: Ring Opening of 7-Oxabicycles 361
9.9.5.2.2.2 Method 2: Retro-Diels–Alder Reaction of 7-Oxabicyclo[2.2.1]heptadienes 361
9.9.5.2.2.3 Method 3: Intermolecular Cycloaddition of Alkynes to Oxazoles Followed by Retro-Diels–Alder Reaction 362
9.9.5.2.2.4 Method 4: Cycloaddition of 5-Aminopentynoates with Aldehydes and a-Isocyanoacetamides Followed by Retro-Diels–Alder Reaction 363
9.9.5.2.2.5 Method 5: Synthesis from (7-Oxabicyclo[2.2.1]hept-5-en-2-ylidene)-amines by Grob Fragmentation 364
9.9.5.2.3 Ring Contraction 365
9.9.5.2.3.1 Method 1: Synthesis from Furo[3,4-c]pyranones 365
9.9.5.2.3.2 Method 2: Synthesis from 3,6-Dihydro-1,2-dioxins 366
9.9.5.2.3.3 Method 3: Synthesis from Sugar Derivatives 366
9.9.5.3 Aromatization 367
9.9.5.3.1 Method 1: Synthesis by Elimination 367
9.9.5.3.2 Method 2: Oxidation of Dihydrofurans 369
9.9.5.4 Synthesis by Substituent Modification 369
9.9.5.4.1 Substitution of Hydrogen 369
9.9.5.4.1.1 Method 1: Introduction of Aminoalkyl Groups with N-Sulfinyl-4-toluene-sulfonamide and Zinc(II) Chloride 369
9.9.5.4.1.2 Method 2: Introduction of a Hydroxymethyl Group by Friedel–Crafts Reaction 370
9.9.5.4.1.3 Method 3: Introduction of Aryl, Alkynyl, Alkyl, or Hydroxymethyl Groups by Addition/Oxidative Rearrangement 371
9.9.5.4.1.4 Method 4: Introduction of Alk-1-enyl Groups by Coupling with Alkenes or Alkynes 373
9.9.5.4.1.5 Method 5: Introduction of Alkyl Groups by Reaction with Activated Alkenes 374
9.9.5.4.1.6 Method 6: Introduction of Aryl Groups by Coupling with Aryl Halides 376
9.9.5.4.1.7 Method 7: Introduction of Alkyl Groups by Lewis Acid or Metal-Catalyzed Reactions 377
9.9.5.4.1.8 Method 8: Introduction of exo-Methylene Groups by Catalytic Inter- or Intramolecular Hydroarylation of Unactivated Triple Bonds 378
9.9.5.4.1.9 Method 9: Introduction of Halogen Substituents 379
9.9.5.4.1.10 Method 10: Ammonium Cerium(IV) Nitrate Catalyzed Radical Dimerization 379
9.9.5.4.2 Substitution of Metals 379
9.9.5.4.2.1 Method 1: Replacement of Lithium by a Hydroxymethyl Group 379
9.9.5.4.2.2 Method 2: Replacement of Lithium by a Carbonyl Group 380
9.9.5.4.2.3 Method 3: Replacement of Lithium by Alkynyl Groups via Intermediate (Butyltellanyl)furans 381
9.9.5.4.2.4 Method 4: Replacement of Lithium by an Alkyl Group via Intermediate Stannanes (Stille Coupling) 382
9.9.5.4.2.5 Method 5: Replacement of Lithium by an Aryl or Alkynyl Group via Intermediate Boronates (Suzuki Coupling) 382
9.9.5.4.2.6 Method 6: Replacement of Lithium by Deuterium 384
9.9.5.4.2.7 Method 7: Replacement of Lithium or Magnesium by Carbonyl, Aryl, or Alkenyl Groups via Intermediate Furylzinc Compounds 384
9.9.5.4.2.8 Method 8: Replacement of Lithium by an Allyl Group 385
9.9.5.4.2.9 Method 9: Replacement of Lithium by a Silyl Group 385
9.9.5.4.2.10 Method 10: Replacement of Lithium by a Carbonyl Group via a Furyltitanium 386
9.9.5.4.3 Substitution of Carbon Functionalities 386
9.9.5.4.3.1 Method 1: Curtius Rearrangement of Furan-2-carboxylic Acids 387
9.9.5.4.4 Substitution of Heteroatoms 388
9.9.5.4.4.1 Method 1: Reaction of Halofurans with Heteroatom Nucleophiles 388
9.9.5.4.4.2 Method 2: Reaction of Halofurans with Carbonyl Electrophiles 388
9.9.5.4.4.3 Method 3: Reactions of Halofurans with Alkenes 389
9.9.5.4.4.4 Method 4: Nucleophilic Aromatic Substitution of Activated 2-Methoxyfurans with Grignard Reagents 389
9.9.5.4.5 Modification of a-Substituents 390
9.9.5.4.5.1 Method 1: Multicomponent Type II Anion Relay Chemistry of 2-(tert-Butyldimethylsilyl)furan-3-carbaldehyde 390
9.9.5.4.5.2 Method 2: Wittig Rearrangement of 3-Furylmethyl Ethers 390
9.9.5.4.5.3 Method 3: Ene Reaction of 2-Methylene-2,3-dihydrofurans 391
9.9.5.4.5.4 Method 4: Pummerer-Type Reaction of (Phenylsulfinyl)furans 392
9.9.5.4.5.5 Method 5: 1,5-Electrocyclization of Carbene-Derived Ylides from N-(2-Furylmethylene)anilines 393
9.10 Product Class 10: Thiophenes, Thiophene 1,1-Dioxides, and Thiophene 1-Oxides 402
9.10.4 Thiophenes, Thiophene 1,1-Dioxides, and Thiophene 1-Oxides 402
9.10.4.1 Thiophenes 402
9.10.4.1.1 Synthesis by Ring-Closure Reactions 402
9.10.4.1.1.1 By Formation of Two S--C Bonds and One C--C Bond 402
9.10.4.1.1.1.1 Fragment S and Two C--C Fragments 402
9.10.4.1.1.1.1.1 Method 1: Synthesis from a Diphosphorylacetylene and Sodium Hydrosulfide Hydrate 402
9.10.4.1.1.2 By Formation of Two S--C Bonds 403
9.10.4.1.1.2.1 Fragments C--C--C--C and S 403
9.10.4.1.1.2.1.1 Method 1: Reaction of a,ß-Unsaturated Nitriles with Sulfur (The Gewald Synthesis) 403
9.10.4.1.1.3 By Formation of Two C--C Bonds 404
9.10.4.1.1.3.1 Fragments C--S--C and C--C 404
9.10.4.1.1.3.1.1 Method 1: Reaction of 3-Thia-1,5-dicarbonyl Compounds or Equivalents with 1,2-Dicarbonyl Compounds (The Hinsberg Synthesis) 404
9.10.4.1.2 Synthesis by Substituent Modification 406
9.10.4.1.2.1 Substitution of Hydrogen 406
9.10.4.1.2.1.1 Method 1: Hydrogen–Deuterium Exchange 406
9.10.4.1.2.1.2 Method 2: Introduction of Formyl Groups 406
9.10.4.1.2.1.2.1 Variation 1: Formylation with Hexamethylenetetramine in Polyphosphoric Acid 406
9.10.4.1.2.1.2.2 Variation 2: Metalation of Thiophenes Followed by Formylation with N-Formylpiperidine 407
9.10.4.1.2.1.3 Method 3: Introduction of Acyl Groups 408
9.10.4.1.2.1.3.1 Variation 1: Acylation of Thiophene with Anhydrides 408
9.10.4.1.2.1.3.2 Variation 2: Acylation of Thiophene with Acyl Chlorides 409
9.10.4.1.2.1.3.3 Variation 3: Acylation of Thiophene with an Ester 410
9.10.4.1.2.1.3.4 Variation 4: Acylation of Thiophene with Carboxylic Acids 410
9.10.4.1.2.1.4 Method 4: Introduction of Chloromethyl Groups 411
9.10.4.1.2.1.5 Method 5: Introduction of Alkylamino Groups 412
9.10.4.1.2.1.6 Method 6: Introduction of Allyl, Alk-1-enyl, or Alk-1-ynyl Groups 413
9.10.4.1.2.1.7 Method 7: Introduction of Aryl Groups 414
9.10.4.1.2.1.7.1 Variation 1: One-Pot C--H Borylation/Suzuki–Miyaura Cross Coupling 414
9.10.4.1.2.1.7.2 Variation 2: Palladium-Catalyzed Direct Arylation 416
9.10.4.1.2.1.8 Method 8: Introduction of Alkyl Groups 417
9.10.4.1.2.1.8.1 Variation 1: Gold(III)-Catalyzed Intermolecular Hydroarylation 417
9.10.4.1.2.1.8.2 Variation 2: Dichlorobis(.5-cyclopentadienyl)zirconium(IV)-Catalyzed Alkylation 417
9.10.4.1.2.1.8.3 Variation 3: Friedel–Crafts Alkylation of Thiophenes 418
9.10.4.1.2.1.9 Method 9: Halogenation 419
9.10.4.1.2.1.10 Method 10: Nitration 420
9.10.4.1.2.2 Substitution of Metals 421
9.10.4.1.2.2.1 Method 1: Substitution Reactions Involving Organostannanes (The Stille Reaction) 421
9.10.4.1.2.2.2 Method 2: Substitution Reactions Involving Organozinc Derivatives (The Negishi Reaction) 422
9.10.4.1.2.2.3 Method 3: Substitution Reactions Involving Organoboron Derivatives (The Suzuki Reaction) 423
9.10.4.1.2.2.4 Method 4: Substitution Reactions Involving Organomagnesium Derivatives (The Kumada Reaction) 425
9.10.4.1.2.3 Substitution of Heteroatoms 426
9.10.4.1.2.3.1 Method 1: Substitution of Halogens by Hydrogen 426
9.10.4.1.2.3.2 Method 2: Substitution of Halogens by Alkoxy Groups 427
9.10.4.1.2.3.3 Method 3: Metal-Assisted Cross Coupling of Halothiophenes with Alkenes 427
9.10.4.1.2.3.3.1 Variation 1: Cross Coupling of Halothiophenes with Alkenes in the Presence of a Palladium/Tetraphosphine Catalyst 427
9.10.4.1.2.3.3.2 Variation 2: Cross Coupling of Halothiophenes with Alkenes in the Presence of Palladium-Containing Nanostructured Silica Functionalized with Pyridine Sites 428
9.10.4.1.2.3.3.3 Variation 3: Palladium-Catalyzed Heck Reactions of Halothiophenes with Electron-Rich Alkenes in an Ionic Liquid 429
9.10.4.1.2.3.4 Method 4: Metal-Assisted Cross Coupling of Halothiophenes with Arenes 430
9.10.4.1.2.3.4.1 Variation 1: Suzuki Cross Coupling of Halothiophenes with Arenes in the Presence of a Palladium/Tetraphosphine Catalyst 430
9.10.4.1.2.3.4.2 Variation 2: Suzuki Cross Coupling of Halothiophenes with Arenes in the Presence of a Biarylmonophosphine Ligand 431
9.10.4.1.2.3.4.3 Variation 3: Site-Selective Suzuki–Miyaura Reactions of 2,3,5-Tribromothiophene 432
9.10.4.1.2.3.4.4 Variation 4: Suzuki-Type Cross Coupling of Halothiophenes with Arenes in the Presence of Boronates 434
9.10.4.1.2.3.4.5 Variation 5: Stille Cross Coupling of Halothiophenes with Organostannanes in the Presence of a ß-Oxoiminate(phosphine)palladium Catalyst 435
9.10.4.1.2.3.5 Method 5: Metal-Assisted Cross Coupling of Halothiophenes with Alkynes 436
9.10.4.1.2.3.6 Method 6: Palladium-Catalyzed Cyanation Reactions of Halothiophenes 437
9.10.4.1.2.3.7 Method 7: Copper-Catalyzed Amination of Halothiophenes 439
9.10.4.1.2.3.8 Method 8: Substitution of Diaryliodonium Bromides 440
9.10.4.1.2.4 Modification of a-Substituents 440
9.10.4.1.2.4.1 Method 1: Mitsunobu Reaction of Thiophenones 440
9.10.4.1.2.4.2 Method 2: Decarboxylation 442
9.10.4.2 Oligothiophenes 443
9.10.4.2.1 Synthesis by Ring-Closure Reactions 443
9.10.4.2.1.1 By Formation of Two S--C Bonds 443
9.10.4.2.1.1.1 Fragments C--C--C--C and S 443
9.10.4.2.1.1.1.1 Method 1: Reaction of Buta-1,3-diynes with Sulfides as Sulfuration Reagents 443
9.10.4.2.1.1.1.2 Method 2: Reaction of 1,4-Diketones with Sulfur Reagents and Cyclization 444
9.10.4.2.2 Synthesis by Ring Transformation 445
9.10.4.2.2.1 Ring Contraction 445
9.10.4.2.2.1.1 Method 1: Synthesis from 1,2-Dithiins by Oxidative Coupling/Dechalcogenation with Copper Nanopowder 445
9.10.4.2.3 Synthesis by Substituent Modification 447
9.10.4.2.3.1 Substitution of Hydrogen 447
9.10.4.2.3.1.1 Method 1: Oxidative Coupling Reactions 447
9.10.4.2.3.1.2 Method 2: Direct Arylation Methods Involving Metal Catalysis 451
9.10.4.2.3.1.2.1 Variation 1: Aryl--Aryl Bond Formation via Coupling of Two C--H Bonds 451
9.10.4.2.3.2 Substitution of Metals 451
9.10.4.2.3.2.1 Method 1: Substitution Reactions Involving Organostannanes (The Stille Reaction) 451
9.10.4.2.3.2.1.1 Variation 1: Palladium-Catalyzed Stille Cross-Coupling Reactions 451
9.10.4.2.3.2.1.2 Variation 2: Palladium-Catalyzed, Copper(II) Oxide Modified Stille Cross-Coupling Reactions 454
9.10.4.2.3.2.1.3 Variation 3: Palladium-Catalyzed, Solid-Phase Stille Cross-Coupling Reactions 455
9.10.4.2.3.2.2 Method 2: Substitution Reactions Involving Organozinc Derivatives 456
9.10.4.2.3.2.3 Method 3: Substitution Reactions Involving Organoboron Derivatives (The Suzuki Reaction) 458
9.10.4.2.3.2.3.1 Variation 1: Tetrakis(triphenylphosphine)palladium(0)-Assisted Suzuki Cross Coupling under Basic Conditions 458
9.10.4.2.3.2.3.2 Variation 2: Microwave-Assisted Palladium Catalysis Using Silica- and Chitosan-Supported Palladium Complexes 460
9.10.4.2.3.2.3.3 Variation 3: A “Base-Free” Tetrakis(triphenylphosphine)palladium(0)-Assisted Suzuki Cross-Coupling Protocol Involving a Triethylborate Salt 461
9.10.4.2.3.2.4 Method 4: Substitution Reactions Involving Organomagnesium Derivatives 463
9.10.4.2.3.3 Substitution of Heteroatoms 464
9.10.4.2.3.3.1 Method 1: Introduction of Aryl Groups 464
9.10.4.2.3.3.2 Method 2: Palladium-Assisted Coupling Reactions 465
9.10.4.3 Thiophene 1,1-Dioxides 466
9.10.4.3.1 Synthesis by Ring Transformation 466
9.10.4.3.1.1 Oxidation 466
9.10.4.3.1.1.1 Method 1: Oxidation of Thiophenes 466
9.10.4.3.2 Aromatization 468
9.10.4.3.2.1 Method 1: Synthesis from 3-Hydroxy-2,3-dihydrothieno[3,2-b]thiophene-1,1-Dioxides by Dehydration 468
Volume 20: Three Carbon--Heteroatom Bonds: Acid Halides Carboxylic Acids and Acid Salts
20.5 Product Class 5: Carboxylic Acid Esters 476
20.5.1.7.15 Synthesis with Retention of the Functional Group 476
20.5.1.7.15.1 Conjugate Addition to a,ß-Unsaturated Esters 476
20.5.1.7.15.1.1 Method 1: Conjugate Addition of Organometallic Reagents 476
20.5.1.7.15.1.1.1 Variation 1: Conjugate Addition of Organocopper Reagents 476
20.5.1.7.15.1.1.2 Variation 2: Conjugate Addition of Grignard Reagents 478
20.5.1.7.15.1.1.3 Variation 3: Conjugate Addition of Organolithium Reagents 481
20.5.1.7.15.1.2 Method 2: Conjugate Addition of Other Carbon Nucleophiles 483
20.5.1.7.15.1.2.1 Variation 1: Conjugate Addition of Enolates 483
20.5.1.7.15.1.2.2 Variation 2: Conjugate Addition of Malonates and Derivatives 484
20.5.1.7.15.1.2.3 Variation 3: Conjugate Addition of Terminal Alkynes 485
20.5.1.7.15.1.3 Method 3: Conjugate Addition of Organosilane Reagents 485
20.5.1.7.15.1.4 Method 4: Conjugate Addition of Organoborane Reagents 486
20.5.1.7.15.1.5 Method 5: Conjugate Addition of Boronate Derivatives 490
20.5.1.7.15.1.6 Method 6: Conjugate Addition of Amines 491
20.5.1.7.15.1.7 Method 7: Conjugate Addition of O- and S-Nucleophiles 494
Volume 39: Sulfur, Selenium, and Tellurium 500
39.1 Product Class 1: Alkanesulfonic Acids and Acyclic Derivatives 500
39.1.15 Alkanesulfonic Acids and Acyclic Derivatives 500
39.1.15.1 Applications of Alkanesulfonyl Halides in Organic Synthesis 500
39.1.15.1.1 Method 1: Protection of Alcohols 500
39.1.15.1.2 Method 2: Protection of Amines 501
39.1.15.1.3 Method 3: Synthesis of Alkanethiols 501
39.1.15.1.4 Method 4: Synthesis of Dialkyl Disulfides 501
39.1.15.1.5 Method 5: Synthesis of Sulfinic Acids and Salts 502
39.1.15.1.6 Method 6: Synthesis of Alkanesulfinate Esters 502
39.1.15.1.7 Method 7: Synthesis of Alkanethiosulfonic Acids and Alkanethiosulfinate Esters 502
39.1.15.1.8 Method 8: Synthesis of Sulfones 502
39.1.15.1.8.1 Variation 1: Reactions of Alkanesulfonyl Chlorides with Organometallic Compounds 502
39.1.15.1.8.2 Variation 2: Synthesis of Alkyl Aryl Sulfones 504
39.1.15.1.8.3 Variation 3: Addition of Sulfonyl Halides to Multiple Bonds 505
39.1.15.1.8.4 Variation 4: Synthesis of ß-Substituted Sulfones 506
39.1.15.1.9 Method 9: Synthesis of Sulfur Heterocycles 511
39.1.15.1.10 Method 10: Formation of C--C Bonds Using Alkanesulfonyl Halides 517
39.1.15.1.11 Method 11: Formation of C==C Bonds Using Alkanesulfonyl Halides 521
39.1.15.1.12 Method 12: Transformation of Alcohols into Alkyl Chlorides and Chlorination Reactions 524
39.1.15.1.13 Method 13: Cyclization Reactions via Acyliminium Ion Formation 526
39.1.15.1.14 Method 14: Pyrrolidine Ring Formation 527
39.1.15.1.15 Method 15: Epoxide Ring Formation 527
39.1.15.1.16 Method 16: Lactone Inversion 528
39.1.15.1.17 Method 17: Formation of Aldehydes via Rearrangement of Thioacetals 528
Author Index 532
Abbreviations 556
List of All Volumes 562