Science of Synthesis: Cross Coupling and Heck-Type Reactions Vol. 2 (eBook)

Carbon-Heteroatom Cross Coupling and C-C Cross Coupling of Acidic C-H Nucleophiles

John Wolfe (Herausgeber)

eBook Download: EPUB

2014 | 1. Auflage
744 Seiten
Thieme (Verlag)
978-3-13-179081-1 (ISBN)

Infos

<p>In <em>Science of Synthesis: Cross Coupling and Heck-Type Reactions</em>, expert authors present and discuss the best and most reliable methods currently available for the formation of new carbon-carbon and carbon-heteroatom bonds using these reactions, highlighted with representative experimental procedures. Together, the three volumes of <em>Cross Coupling and Heck-Type Reactions</em> provide an extensive overview of the current state of the art in this field of central importance in modern chemistry, and are an invaluable resource for the practicing synthetic organic chemist.</p><p>This volume is focused on the formation of carbon-heteroatom bonds and carbon-carbon bonds of acidic C-H nucleophiles. The chapters are intended to provide the reader with a practical guide to the most efficient, reliable, and useful metal-catalyzed cross-coupling reactions that generate C-N, C-P, C-O, C-S, C-B, C-Si, C-CN, and C-F bonds, and C-C bonds adjacent to carbonyl functional groups. The most up-to-date and modern methods are included, including those that facilitate replacement of typically unreactive C-H bonds with carbon-heteroatom bonds.</p><p> This volume is part of a 3-volume set: </p><p><a href='http://www.thieme.com/index.php?page=shop.product_details&amp;flypage=flypage.tpl&amp;product_id=1498&amp;category_id=11&amp;keyword=cross+Coupling&amp;option=com_virtuemart&amp;Itemid=53'>Cross Coupling and Heck-Type Reactions Workbench Edition</a></p><p><a href='http://www.thieme-chemistry.com/en/products/reference-works/science-of-synthesis.html'>General information about Science of Synthesis</a></p>

Inhalt

Science of Synthesis: Cross Coupling and Heck-Type Reactions 2 – Carbon—HeteroatomCross Coupling and C—C Cross Coupling of Acidic C—H Nucleophiles 1
Organizational Structure of Science of Synthesis 2
Science of Synthesis Reference Library 3
Title page 5
Imprint 7
Preface 8
Volume Editor's Preface 10
Cross Coupling and Heck-Type Reactions Volumes 12
Abstracts 14
Overview 22
Table of Contents 24
Introduction 38
2.1 C--N Bond-Forming Reactions 46
2.1.1 C--N Bond-Forming Reactions of Alkylamines 46
2.1.1.1 Alkylamines with Aryl and Alkenyl Electrophiles 46
2.1.1.1.1 Copper-Catalyzed Coupling of Alkylamines with Aryl Halides 46
2.1.1.1.1.1 Using Amino Acids as Ligands 49
2.1.1.1.1.2 Using Ethylene Glycol as a Ligand 49
2.1.1.1.1.3 Using 2-Acylcyclohexanones as Ligands 51
2.1.1.1.1.4 Using 8-Hydroxyquinoline 1-Oxide as a Ligand 52
2.1.1.1.1.5 Room-Temperature Coupling of Amines Promoted by Ionic Organic Bases 53
2.1.1.1.1.6 Environmentally Friendly Ullmann Amination Reactions 54
2.1.1.1.1.6.1 Ligand-Free Copper-Catalyzed N-Arylation Reactions of Amino Acids and Amino Alcohols 54
2.1.1.1.1.6.2 Heterogeneous Coupling of Amines and Aryl Halides Using Copper--Aluminum Hydrotalcite 56
2.1.1.1.1.6.3 Aqueous-Phase Coupling of Amines and Aryl Halides without Ligands or Organic Solvents 56
2.1.1.1.1.7 Synthesis of Primary Anilines by Coupling of Aryl Halides with Aqueous Ammonia 57
2.1.1.1.1.7.1 Using Copper(I) Oxide without Ligands or Base 58
2.1.1.1.1.7.2 Using Copper(I) Iodide Nanoparticles without Ligands or Organic Solvents 59
2.1.1.1.1.8 Copper-Catalyzed Coupling of Alkylamines with Boronic Acid Derivatives (Chan--Lam--Evans Reaction) 60
2.1.1.1.2 Palladium-Catalyzed Coupling of Alkylamines with Aryl and Alkenyl Halides 61
2.1.1.1.2.1 Palladium-Catalyzed Coupling of Alkylamines with Aryl Halides 64
2.1.1.1.2.1.1 Using Dialkyl(biaryl)phosphine Ligands 64
2.1.1.1.2.1.2 Using N-Heterocyclic Carbene Ligands 66
2.1.1.1.2.1.3 Using a Multiligand System 67
2.1.1.1.2.1.4 Using a Bisphosphine Ligand 69
2.1.1.1.2.2 Palladium-Catalyzed Coupling of Alkylamines with Alkenyl Halides 70
2.1.1.1.2.3 Synthesis of Aniline Derivatives by Coupling of Ammonia with Aryl Halides 71
2.1.1.1.2.3.1 Using a Bisphosphine Ligand 72
2.1.1.1.2.3.2 Using Biarylphosphine Ligands 73
2.1.1.1.2.3.3 Using a P,N-Ligand 74
2.1.1.2 Alkylamines with Hetaryl Electrophiles 80
2.1.1.2.1 Palladium-Catalyzed Hetaryl Amination 80
2.1.1.2.1.1 Benzimidazole Electrophiles 80
2.1.1.2.1.2 Benzothiophene Electrophiles 81
2.1.1.2.1.3 Benzothiazole Electrophiles 82
2.1.1.2.1.4 Carbazole Electrophiles 84
2.1.1.2.1.5 Furan Electrophiles 85
2.1.1.2.1.6 Indole Electrophiles 87
2.1.1.2.1.7 Isoquinoline Electrophiles 88
2.1.1.2.1.8 Oxazole Electrophiles 89
2.1.1.2.1.9 Phenanthroline Electrophiles 91
2.1.1.2.1.10 Purine Electrophiles 91
2.1.1.2.1.11 Pyrazine Electrophiles 92
2.1.1.2.1.12 Pyrazole Electrophiles 93
2.1.1.2.1.13 Pyridazine Electrophiles 94
2.1.1.2.1.14 Pyridine Electrophiles 95
2.1.1.2.1.14.1 2-Halo- or 2-(Tosyloxy)pyridines 95
2.1.1.2.1.14.1.1 2-Chloropyridines 95
2.1.1.2.1.14.1.2 2-Bromopyridines 97
2.1.1.2.1.14.1.3 2-Iodo- and 2-(Tosyloxy)pyridines 101
2.1.1.2.1.14.2 3-Halopyridines 102
2.1.1.2.1.14.2.1 3-Chloropyridines 102
2.1.1.2.1.14.2.2 3-Bromopyridines 103
2.1.1.2.1.14.2.3 3-Iodo- and 3-(Tosyloxy)pyridines 104
2.1.1.2.1.14.3 4-Halopyridines 105
2.1.1.2.1.15 Pyridinone Electrophiles 107
2.1.1.2.1.16 Pyrimidine Electrophiles 107
2.1.1.2.1.17 Pyrrole Electrophiles 112
2.1.1.2.1.18 Quinoline Electrophiles 113
2.1.1.2.1.19 Thiazole Electrophiles 120
2.1.1.2.1.20 Thiophene Electrophiles 121
2.1.1.2.1.21 Triazole Electrophiles 122
2.1.1.2.1.22 Quinolin-2-one Electrophiles 123
2.1.1.2.2 Copper-Catalyzed Hetaryl Amination 124
2.1.1.2.2.1 Benzimidazole Electrophiles 124
2.1.1.2.2.2 Benzothiophene Electrophiles 125
2.1.1.2.2.3 Pyrazole Electrophiles 126
2.1.1.2.2.4 Pyridine Electrophiles 126
2.1.1.2.2.5 Pyrimidine Electrophiles 128
2.1.1.2.2.6 Thiazole Electrophiles 130
2.1.1.2.2.7 Thiophene Electrophiles 131
2.1.1.2.2.8 Benzothiazole Electrophiles 132
2.1.1.2.2.9 Quinoline Electrophiles 133
2.1.1.2.3 Other-Metal-Catalyzed Hetaryl Amination 134
2.1.1.2.3.1 Benzoxazole Electrophiles 134
2.1.1.2.3.2 Pyridine Electrophiles 135
2.1.1.2.3.3 Other Hetaryl Electrophiles 139
2.1.2 C--N Bond-Forming Reactions of Aryl- and Hetarylamines 144
2.1.2.1 Aryl- and Hetarylamines with Aryl and Alkenyl Electrophiles 144
2.1.2.1.1 Primary Aromatic Amines 148
2.1.2.1.1.1 Aryl Iodides 148
2.1.2.1.1.1.1 Palladium-Catalyzed Coupling Reactions 148
2.1.2.1.1.1.2 Copper-Catalyzed Coupling Reactions 150
2.1.2.1.1.2 Aryl Bromides 151
2.1.2.1.1.2.1 Palladium-Catalyzed Coupling Reactions 151
2.1.2.1.1.2.2 Copper-Catalyzed Coupling Reactions 156
2.1.2.1.1.3 Aryl Chlorides 158
2.1.2.1.1.4 Aryl Sulfonates 163
2.1.2.1.1.4.1 Aryl Trifluoromethanesulfonates and Nonafluorobutanesulfonates 163
2.1.2.1.1.4.2 Aryl Benzenesulfonates and 4-Toluenesulfonates 164
2.1.2.1.1.4.3 Aryl Methanesulfonates 165
2.1.2.1.1.5 Arylboronic Acids/Esters (Chan--Lam--Evans Coupling) 166
2.1.2.1.1.6 Alkenyl Halides 167
2.1.2.1.2 Secondary Aromatic Amines 169
2.1.2.1.2.1 Aryl Iodides 169
2.1.2.1.2.1.1 Palladium-Catalyzed Coupling Reactions 169
2.1.2.1.2.1.2 Copper-Catalyzed Coupling Reactions 170
2.1.2.1.2.2 Aryl Bromides 172
2.1.2.1.2.2.1 Palladium-Catalyzed Coupling Reactions 172
2.1.2.1.2.2.2 Copper-Catalyzed Coupling Reactions 177
2.1.2.1.2.3 Aryl Chlorides 178
2.1.2.1.2.4 Aryl Sulfonates 183
2.1.2.1.2.4.1 Aryl Trifluoromethanesulfonates 183
2.1.2.1.2.4.2 Aryl Benzenesulfonates 184
2.1.2.1.2.4.3 Aryl Methanesulfonates 185
2.1.2.1.2.5 Arylboronic Acids/Esters (Chan--Lam--Evans Coupling) 186
2.1.2.1.2.6 Alkenyl Halides 186
2.1.2.1.2.6.1 Palladium-Catalyzed Coupling Reactions 186
2.1.2.1.2.6.2 Copper-Catalyzed Coupling Reactions 188
2.1.2.1.2.7 Alkenyl Sulfonates 188
2.1.2.1.3 Primary Heteroaromatic Amines 189
2.1.2.1.3.1 Aryl Iodides 189
2.1.2.1.3.1.1 Palladium-Catalyzed Coupling Reactions 189
2.1.2.1.3.1.2 Copper-Catalyzed Coupling Reactions 191
2.1.2.1.3.2 Aryl Bromides 193
2.1.2.1.3.2.1 Palladium-Catalyzed Coupling Reactions 193
2.1.2.1.3.2.2 Copper-Catalyzed Coupling Reactions 197
2.1.2.1.3.3 Aryl Chlorides 198
2.1.2.1.3.4 Aryl Sulfonates 200
2.1.2.1.3.5 Arylboronic Acids/Esters (Chan--Lam--Evans Coupling) 201
2.1.2.1.4 Secondary Heteroaromatic Amines 202
2.1.2.1.4.1 Aryl Iodides 202
2.1.2.1.4.2 Aryl Bromides 204
2.1.2.1.4.2.1 Palladium-Catalyzed Coupling Reactions 204
2.1.2.1.4.2.2 Copper-Catalyzed Coupling Reactions 205
2.1.2.1.4.3 Aryl Chlorides 205
2.1.2.2 Aryl- and Hetarylamines with Hetaryl Electrophiles 210
2.1.2.2.1 Palladium-Catalyzed Methods 210
2.1.2.2.1.1 Reactions of Primary Arylamines with Hetaryl Electrophiles 210
2.1.2.2.1.2 Reactions of Secondary Arylamines with Hetaryl Electrophiles 221
2.1.2.2.1.3 Reactions of Hetarylamines with Hetaryl Electrophiles 225
2.1.2.2.2 Copper-Catalyzed Methods 227
2.1.2.2.3 Conclusions and Perspectives 229
2.1.3 C--N Bond-Forming Reactions of Hetarenes 232
2.1.3.1 Copper-Catalyzed Reactions 232
2.1.3.1.1 N-Arylation of Hetarenes 232
2.1.3.1.1.1 With Aryl Halides 232
2.1.3.1.1.2 With Arylboronic Acid Derivatives 239
2.1.3.1.1.3 With Other Arylmetal Complexes 241
2.1.3.1.2 N-Vinylation of Hetarenes 243
2.1.3.2 Palladium-Catalyzed Reactions 244
2.1.3.2.1 N-Arylation of Hetarenes 244
2.1.3.2.2 N-Vinylation of Hetarenes 245
2.1.3.3 Reactions Catalyzed by Other Transition Metals 247
2.1.3.3.1 Cadmium-Catalyzed Reactions 247
2.1.3.3.2 Iron-Catalyzed Reactions 248
2.1.3.3.3 Iron/Copper Cocatalyzed Reactions 249
2.1.4 C--N Bond-Forming Reactions of Amides and Carbamates 252
2.1.4.1 Aryl and Hetaryl Electrophiles 253
2.1.4.1.1 Copper-Catalyzed Intermolecular Coupling with Aryl and Hetaryl Halides 254
2.1.4.1.2 Copper-Catalyzed Intramolecular Coupling of Aryl and Hetaryl Halides 261
2.1.4.1.3 Palladium-Catalyzed Coupling with Aryl and Hetaryl Halides 265
2.1.4.1.4 Palladium-Catalyzed Coupling with Aryl and Hetaryl Sulfonates 272
2.1.4.2 Alkenyl and Allenyl Electrophiles 275
2.1.4.2.1 Copper-Catalyzed Coupling with Alkenyl and Allenyl Electrophiles 276
2.1.4.2.2 Palladium-Catalyzed Coupling with Alkenyl Electrophiles 280
2.1.4.3 Alkynyl Electrophiles 283
2.1.4.4 Oxidative Coupling with Boronic Acids and Related Reagents 284
2.1.5 C--N Bond-Forming Reactions of Sulfonamides, Sulfoximides, and Other Nitrogen Nucleophiles 292
2.1.5.1 C--N Bond-Forming Reactions of Sulfonamides 292
2.1.5.1.1 Metal-Catalyzed N-Alkylation of Sulfonamides with Alcohols 292
2.1.5.1.2 N-Vinylation of Sulfonamides 294
2.1.5.1.3 N-Alkynylation of Sulfonamides and Intramolecular Cyclizations of Alkynyl Sulfonamides 296
2.1.5.1.4 N-Allenylation of Allylic Sulfonamides and Cyclization of Allenic Sulfonamides 298
2.1.5.1.5 N-Arylation of Sulfonamides 301
2.1.5.1.5.1 Intermolecular N-Arylation 301
2.1.5.1.5.2 Intramolecular N-Arylation 303
2.1.5.2 C--N Bond-Forming Reactions of Sulfoximides 304
2.1.5.2.1 Transition-Metal-Catalyzed Arylation of Sulfoximides 304
2.1.5.2.1.1 Palladium-Catalyzed Reactions 304
2.1.5.2.1.2 Nickel-Catalyzed Reactions 306
2.1.5.2.1.3 Copper-Catalyzed Reactions 306
2.1.5.2.1.4 Iron-Catalyzed Reactions 307
2.1.5.2.2 N-Vinylation of Sulfoximides 308
2.1.5.2.3 2,1-Benzothiazine Synthesis 308
2.1.5.3 C--N Bond Formation Using Other Nitrogen Nucleophiles 309
2.1.5.3.1 Metal-Promoted Synthesis of N-Substituted Sulfamides 309
2.1.5.3.2 Copper-Mediated Arylation of Sulfonimidamides 311
2.1.5.3.3 Metal-Catalyzed Guanidinylation 312
2.1.5.3.4 Metal-Catalyzed Arylation of Ureas 315
2.1.6 C--N Bond-Forming Reactions of C--H Electrophiles 320
2.1.6.1 sp2-C--N Bond Formation 320
2.1.6.1.1 Azides as the Nitrogen-Atom Source 320
2.1.6.1.2 Nitro Reagents as the Nitrogen-Atom Source 328
2.1.6.1.3 Acidic Amines as the Nitrogen-Atom Source 330
2.1.6.1.4 Neutral Amines as the Nitrogen-Atom Source 337
2.1.6.1.5 Amidines, Imines, and Oximes as the Nitrogen-Atom Source 338
2.1.6.2 sp3-C--N Bond Formation 344
2.1.6.2.1 Sulfamate Esters or Sulfamides as the Nitrogen-Atom Source 344
2.1.6.2.2 Sulfonimidamides as the Nitrogen-Atom Source 351
2.1.6.2.3 Chloramine-T or Bromamine-T as the Nitrogen-Atom Source 354
2.1.6.2.4 N-(Tosyloxy)carbamates as the Nitrogen-Atom Source 356
2.1.6.2.5 Azides as the Nitrogen-Atom Source 359
2.2 C--P Bond-Forming Reactions 368
2.2.1 Cross Coupling of Phosphine Derivatives 369
2.2.1.1 Cross Coupling of Phosphine Oxides 369
2.2.1.1.1 Palladium-Catalyzed Cross Coupling 369
2.2.1.1.1.1 Cross Coupling with a Palladium(II) Catalyst 369
2.2.1.1.1.2 Cross Coupling with a Palladium(0) Catalyst 371
2.2.1.1.2 Nickel- and Copper-Catalyzed Cross Coupling 372
2.2.1.1.2.1 Cross Coupling Using Nickel(II) Chloride 372
2.2.1.1.2.2 Cross Coupling Using Copper(I) Iodide 373
2.2.1.2 Cross Coupling of Phosphines 374
2.2.1.2.1 Cross Coupling of Secondary Phosphines 374
2.2.1.2.1.1 Palladium-Catalyzed Cross Coupling 374
2.2.1.2.1.2 Nickel-Catalyzed Cross Coupling 375
2.2.1.2.1.3 Copper-Catalyzed Cross Coupling 377
2.2.1.2.2 Cross Coupling of Secondary Phosphine--Borane Complexes 379
2.2.1.2.2.1 Palladium-Catalyzed Cross Coupling 379
2.2.1.2.2.1.1 Palladium(0)-Catalyzed Cross Coupling 379
2.2.1.2.2.1.2 Palladium(0)--Copper(I) Catalyzed Aromatic Phosphination 380
2.2.1.2.2.2 Nickel-Catalyzed Cross Coupling 380
2.2.1.2.3 Cross Coupling of Chlorophosphines 381
2.2.1.2.4 Cross Coupling of Silyl- and Stannylphosphines 383
2.2.1.2.4.1 Cross Coupling of Silylphosphines 383
2.2.1.2.4.2 Cross Coupling of Stannylphosphines 383
2.2.1.2.5 Cross Coupling of Primary Phosphines 384
2.2.1.2.6 Cross Coupling of Tertiary Phosphines 385
2.2.1.2.6.1 Nickel-Catalyzed Cross Coupling 385
2.2.1.2.6.2 Palladium-Catalyzed Cross Coupling 386
2.2.1.2.6.2.1 Aryl Exchange 386
2.2.1.2.6.2.2 Synthesis of Phosphonium Salts 387
2.2.2 Cross Coupling of Phosphinate Derivatives 388
2.2.2.1 Cross Coupling of Hypophosphorous Derivatives 388
2.2.2.2 Cross Coupling of H-Phosphinate Esters 391
2.2.3 Cross Coupling of Phosphonate Derivatives 392
2.2.3.1 Palladium-Catalyzed Cross Coupling 392
2.2.3.2 Cross Coupling Using Other Catalysts 393
2.2.4 Cross Coupling of Phosphites, Phosphonites, and Phosphinites 393
2.2.4.1 Cross Coupling of Phosphites 393
2.2.4.1.1 Palladium-Catalyzed Cross Coupling 393
2.2.4.1.2 Nickel-Catalyzed Cross Coupling 394
2.2.4.2 Cross Coupling of Phosphonites and Phosphinites 395
2.3 C--O and C--S Bond-Forming Reactions 400
2.3.1 C--O and C--S Bond-Forming Reactions of C--X Electrophiles 400
2.3.1.1 Palladium-Catalyzed C--O Bond Formation 401
2.3.1.1.1 Synthesis of Diaryl Ethers 401
2.3.1.1.1.1 Coupling of Aryl Halides with Phenols 401
2.3.1.1.2 Synthesis of Alkyl Aryl Ethers 403
2.3.1.1.2.1 Coupling of Primary Alcohols with Aryl Halides 403
2.3.1.1.2.2 Coupling of Secondary Alcohols with Aryl Halides 404
2.3.1.1.2.3 Coupling of Tertiary Alcohols with Aryl Halides 406
2.3.1.1.2.4 Intramolecular Coupling of Alcohols with Aryl Halides 407
2.3.1.2 Copper-Catalyzed C--O Bond Formation 408
2.3.1.2.1 Synthesis of Diaryl Ethers 409
2.3.1.2.1.1 Coupling of Aryl Halides with Phenols 409
2.3.1.2.2 Synthesis of Alkyl Aryl Ethers 409
2.3.1.2.2.1 Coupling of Primary Alcohols with Aryl Halides 409
2.3.1.2.2.2 Coupling of Secondary Alcohols with Aryl Halides 410
2.3.1.2.2.3 Intramolecular Coupling of Alcohols with Aryl Halides 411
2.3.1.2.3 Synthesis of Vinyl Ethers 412
2.3.1.2.3.1 Coupling of Vinyl Halides with Phenols 412
2.3.1.2.4 Synthesis of Other Ethers 413
2.3.1.2.4.1 Coupling of Alcohols with Organoboron Reagents 413
2.3.1.3 Palladium-Catalyzed C--S Bond Formation 415
2.3.1.3.1 Synthesis of Diaryl and Alkyl Aryl Sulfides 415
2.3.1.3.1.1 Coupling of Thiols with Organo Halides or 4-Toluenesulfonates 415
2.3.1.3.2 Synthesis of Aryl Vinyl Sulfides 416
2.3.1.3.2.1 Coupling of Thiols with Vinyl Halides 416
2.3.1.3.3 Synthesis of Benzothiophenes 417
2.3.1.3.3.1 Intramolecular Coupling of Thiols with (gem-Dihalovinyl)arenes 417
2.3.1.3.3.2 Intramolecular Coupling of Thioketones with Aryl Halides 418
2.3.1.3.4 Synthesis of Benzothiazoles 418
2.3.1.3.4.1 Intramolecular Coupling of Thioamides or Thioureas with Aryl Halides 418
2.3.1.3.5 Synthesis of Chiral Diaryl Sulfoxides 419
2.3.1.3.5.1 Coupling of ß-Sulfinyl Esters with Aryl Iodides 419
2.3.1.4 Copper-Catalyzed C--S Bond Formation 420
2.3.1.4.1 Synthesis of Diaryl and Alkyl Aryl Sulfides 420
2.3.1.4.1.1 Coupling of Thiols with Organo Halides 420
2.3.1.4.1.2 Coupling of N-Sulfanylimides with Arylboronic Acids 421
2.3.1.4.1.3 Coupling of Disulfides with Arylboronic Acids 422
2.3.1.4.2 Synthesis of Vinyl Sulfides 424
2.3.1.4.2.1 Intramolecular Coupling of Vinyl Halides with Thiols 424
2.3.1.4.2.2 Coupling of Thiols with Vinyl Halides 425
2.3.1.4.3 Synthesis of Benzothiazoles 426
2.3.1.4.3.1 Intramolecular Coupling of Thiocarbonyls with Aryl Halides 426
2.3.1.5 Other Metal-Catalyzed C--S Bond Formations 426
2.3.1.5.1 Nickel-Catalyzed Synthesis of Diaryl and Alkyl Aryl Sulfides 426
2.3.1.5.1.1 Coupling of Thiols with Organo Halides 426
2.3.1.5.1.2 Coupling of Disulfides with Organo Halides 427
2.3.1.5.2 Cobalt-Catalyzed Synthesis of Diaryl Sulfides 427
2.3.1.5.2.1 Coupling of Thiols with Aryl Halides 427
2.3.1.5.3 Iron-Catalyzed Synthesis of Diaryl Sulfides 428
2.3.1.5.3.1 Coupling of Thiols with Aryl Halides 428
2.3.2 C--O and C--S Bond-Forming Reactions of C---H Electrophiles 432
2.3.2.1 C--O Bond Formation 432
2.3.2.1.1 Palladium(II)-Catalyzed Acyloxylation of C(sp2)--H or C(sp3)--H Bonds with Iodine(III) Reagents 432
2.3.2.1.1.1 Palladium(II)-Catalyzed Acetoxylation of C(sp2)--H Bonds Directed by a Pyridyl Group 432
2.3.2.1.1.2 Palladium(II)-Catalyzed Acetoxylation of C(sp2)--H Bonds Directed by Other Nitrogen-Based Functional Groups 434
2.3.2.1.1.3 Palladium(II)-Catalyzed Acetoxylation of Indole C--H Bonds 436
2.3.2.1.1.4 Palladium(II)-Catalyzed Acetoxylation of C(sp3)--H Bonds 437
2.3.2.1.1.5 Palladium(II)-Catalyzed Acyloxylation of Benzylic C(sp3)--H Bonds 439
2.3.2.1.1.6 Palladium(II)-Catalyzed Acyloxylation Reactions Directed by Diisopropyl(2-pyridyl)silyl Groups 440
2.3.2.1.1.7 Palladium(II)-Catalyzed Acetoxylation in the Absence of a Directing Group 442
2.3.2.1.2 Palladium(II)-Catalyzed Acetoxylation of C(sp3)--H Bonds with Iodine(I) Reagents 443
2.3.2.1.3 Palladium(II)-Catalyzed Oxygenation of C(sp2)--H and C(sp3)--H Bonds with Peroxide Reagents 444
2.3.2.1.3.1 Palladium(II)-Catalyzed Acetoxylation of C(sp2)--H Bonds 444
2.3.2.1.3.2 Palladium(II)-Catalyzed Direct Hydroxylation of C(sp2)--H Bonds 446
2.3.2.1.3.3 Palladium(II)-Catalyzed Acetoxylation of C(sp3)--H Bonds 447
2.3.2.1.4 Palladium(II)-Catalyzed Acetoxylation Using Molecular Oxygen 449
2.3.2.1.5 Palladium(II)-Catalyzed Alkoxylation or Aryloxylation of Arenes 450
2.3.2.1.5.1 Palladium(II)-Catalyzed Intermolecular Alkoxylation of Arene C(sp2)--H Bonds 451
2.3.2.1.5.2 Synthesis of Dihydrobenzofurans by Palladium(II)-Catalyzed Intramolecular C--H Bond Oxygenation 451
2.3.2.1.5.3 Synthesis of Dibenzofurans by Palladium(II)-Catalyzed Intramolecular C--H Bond Oxygenation 452
2.3.2.1.6 Synthesis of Catechols by Palladium(II)-Catalyzed Oxygenation of C--H Bonds 454
2.3.2.1.7 Oxygenation Catalyzed by Transition Metals Other than Palladium 456
2.3.2.1.7.1 Copper(II)-Catalyzed Oxygenation of Arene C(sp2)--H Bonds 456
2.3.2.1.7.2 Synthesis of Benzoxazoles by Intramolecular Copper-Catalyzed Oxygenation of Arene C(sp2)--H Bonds 458
2.3.2.1.7.3 Rhodium-Catalyzed Oxygenation of Arene C(sp2)--H Bonds 460
2.3.2.1.7.4 Gold-Catalyzed Oxygenation of Arene C(sp2)--H Bonds 461
2.3.2.2 C--S Bond Formation 462
2.3.2.2.1 Intramolecular C--S Bond Formation 463
2.3.2.2.1.1 Synthesis of Benzo[b]thiophenes 463
2.3.2.2.1.2 Synthesis of Dibenzothiophenes 465
2.3.2.2.1.3 Synthesis of 2-Arylbenzothiazoles 466
2.3.2.2.1.4 Synthesis of 2-Aminobenzothiazoles 467
2.3.2.2.2 Intermolecular C--S Bond Formation 469
2.3.2.2.2.1 C--S Bond Formation with Arenesulfonyl Chlorides 469
2.3.2.2.2.2 C--S Bond Formation with Dimethyl Sulfoxide 471
2.3.2.2.2.3 C--S Bond Formation with Diaryl or Dialkyl Disulfides 471
2.4 C--B and C--Si Bond-Forming Reactions 476
2.4.1 C--B and C--Si Bond-Forming Reactions of C--X Electrophiles 476
2.4.1.1 C--B Bond-Forming Reactions 477
2.4.1.1.1 Of Aryl--X and Hetaryl--X Electrophiles 477
2.4.1.1.1.1 Using Tetraalkoxydiborons 477
2.4.1.1.1.2 Using Dialkoxyboranes 486
2.4.1.1.1.3 Using In Situ Prepared Dialkoxyboranes 495
2.4.1.1.2 Of Alkenyl--X Electrophiles 497
2.4.1.1.2.1 Using Tetraalkoxydiborons 497
2.4.1.1.2.2 Using Dialkoxyboranes 499
2.4.1.1.3 Of Allyl--X and Benzyl--X Electrophiles 501
2.4.1.1.3.1 Preparation of Allylboronates 501
2.4.1.1.3.2 Preparation of Benzylboronates 503
2.4.1.2 C--Si Bond-Forming Reactions 504
2.4.1.2.1 Of Aryl--X and Hetaryl--X Electrophiles 504
2.4.1.2.1.1 Using Hexaalkyldisilanes 504
2.4.1.2.1.2 Using Trialkoxysilanes 507
2.4.1.2.1.3 Using Trialkylsilanes 512
2.4.1.2.1.4 Using Dialkylsilanes 514
2.4.1.2.2 Of Alkenyl--X and Other Nonaromatic Electrophiles 515
2.4.2 C--B and C--Si Bond-Forming Reactions by C--H Functionalization 522
2.4.2.1 Mechanistic Aspects 523
2.4.2.1.1 C--H Functionalization of Arenes 523
2.4.2.1.2 C--H Functionalization of Alkenes 525
2.4.2.2 C--B Bond-Forming Reactions by C--H Functionalization 527
2.4.2.2.1 C(sp2)--H Functionalization Reactions 527
2.4.2.2.1.1 Synthesis of Aryl- and Hetarylboronates 528
2.4.2.2.1.2 Synthesis of Vinylboronates 531
2.4.2.2.2 C(sp3)--H Functionalization Reactions 538
2.4.2.2.2.1 Synthesis of Allylboronates 539
2.4.2.2.2.2 Synthesis of Benzylboronates 539
2.4.2.2.2.3 Synthesis of Alkylboronates 541
2.4.2.2.3 Sequential and One-Pot Reactions with Catalytically Generated Boronates 542
2.4.2.2.3.1 Synthesis of Phenols, Anilines, and Aryl Halides 542
2.4.2.2.3.2 One-Pot Suzuki--Miyaura Coupling Reactions 546
2.4.2.2.3.3 Allylation of Aldehydes 548
2.4.2.3 C--Si Bond-Forming Reactions by C--H Functionalization 549
2.4.2.3.1 Synthesis of Aryl- and Hetarylsilanes 550
2.4.2.3.2 Synthesis of Vinylsilanes 553
2.4.2.3.3 Synthesis of Allyl-, Benzyl-, and Alkylsilanes 554
2.4.2.4 Summary and Outlook 557
2.5 C--CN Bond-Forming Reactions 560
2.5.1 Cyanation of Aryl Halides and Pseudohalides 561
2.5.2 Cyanation of Arylboronic Acids 572
2.5.3 Cyanation of Vinyl Halides 574
2.5.4 Cyanation of Alkenes and Alkynes 575
2.5.5 Cyanation of a-Aryl Alcohols and Thiols 577
2.5.6 Cyanation through Direct C--H Bond Activation 579
2.6 C--F Bond-Forming Reactions 588
2.6.1 C--F Coupling Reactions with Electrophilic Fluorinating Reagents 588
2.6.1.1 Palladium-Mediated Fluorination of Arylboronic Acids 588
2.6.1.2 Silver-Mediated Fluorination of Arylboronic Acids 590
2.6.1.3 Silver-Mediated Fluorination of Arylsilanes 592
2.6.1.4 Silver-Catalyzed Fluorination of Arylstannanes 593
2.6.1.5 Palladium-Catalyzed Ligand-Directed C--H Fluorination of Arylpyridines 595
2.6.1.6 Palladium-Catalyzed Ligand-Directed C--H Fluorination of Benzylamine Derivatives 596
2.6.1.7 Palladium-Catalyzed Ligand-Directed C--H Fluorination of Benzamide Derivatives 597
2.6.2 C--F Coupling Reactions with Nucleophilic Fluorinating Reagents 599
2.6.2.1 Palladium-Catalyzed Fluorination of Aryl Trifluoromethanesulfonates 599
2.7 C--C Cross-Coupling Reactions of Acidic C--H Nucleophiles 602
2.7.1 C--C Cross-Coupling Reactions of Acidic C--H Nucleophiles with One Activating Group 602
2.7.1.1 Arylation of Ketones 604
2.7.1.1.1 Intermolecular Reactions 604
2.7.1.1.2 Intramolecular Reactions 612
2.7.1.1.3 Stereoselective Reactions 614
2.7.1.1.4 Heteroaromatic Synthesis by Tandem Ketone Arylation/Cyclization 617
2.7.1.2 Arylation of Enones 618
2.7.1.3 Arylation of Aldehydes 619
2.7.1.3.1 Intermolecular Reactions 619
2.7.1.3.2 Intramolecular Reactions 621
2.7.1.4 Arylation of Carboxylic Esters 623
2.7.1.4.1 Intermolecular Reactions 623
2.7.1.4.2 Intramolecular Reactions 630
2.7.1.4.3 Stereoselective Reactions 631
2.7.1.5 Arylation of Carboxylic Amides 634
2.7.1.5.1 Intermolecular Reactions 634
2.7.1.5.2 Intramolecular Reactions 637
2.7.1.5.3 Stereoselective Reactions 641
2.7.1.6 Arylation of Alkanenitriles 644
2.7.1.7 Arylation of Ketimines 648
2.7.1.8 Arylation of Nitroalkanes 649
2.7.1.9 Arylation of Alkyl Sulfones 650
2.7.1.10 Arylation of Alkanesulfonamides 652
2.7.1.11 Arylation of S-Alkylsulfoximides 653
2.7.1.12 Arylation of 1-Alkyl-4-nitrobenzenes 654
2.7.2 C--C Cross-Coupling Reactions of Acidic C--H Nucleophiles with Two Activating Groups 658
2.7.2.1 C--H Nucleophiles with Two Carbonyl Activating Groups 659
2.7.2.1.1 Palladium-Catalyzed Cross Coupling of Aryl Halides or Sulfonates 659
2.7.2.1.2 Copper-Catalyzed Cross Coupling of Aryl Halides 664
2.7.2.2 C--H Nucleophiles with One Carbonyl and One Other Activating Group 673
2.7.2.2.1 Palladium-Catalyzed Cross Coupling of Aryl Halides 673
2.7.2.2.1.1 Coupling with Cyanoacetates 673
2.7.2.2.1.2 Coupling with Sulfones 676
2.7.2.2.1.3 Decarboxylative Coupling with Cyanoacetate Metal Salts 677
2.7.2.2.2 Copper-Catalyzed Cross Coupling of Aryl Halides 679
2.7.2.3 Scope and Limitations of Inter- and Intramolecular C--C Cross-Coupling Reactions 681
Keyword Index 684
Author Index 714
Abbreviations 738
List of All Volumes 746

Produkt-Details

• Erscheint lt. Verlag: 14.5.2014
• Verlagsort: Stuttgart
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Technik
• Schlagworte: Acidic C-H Nucleophiles • Alkylamines • Amides • Arylamines • Carbamates • Carbon-Heteroatom Cross Coupling • C-B Bond • C-C Cross Coupling • C-C Cross-Coupling • C-CN Bond • C-F Bond • Chemische Synthese • chemistry reference work • C-H Functionalization • C-N Bond • C-O Bond • C-P Bond • cross-coupling • Cross Coupling • cross coupling reaction • cross-coupling reaction • C-S Bond • C-Si Bond • Electrophiles • Functional Group • Heck Reaction • Hetarene • hetarenes • Hetarylamines • Mechanism • Method • nitrogen • Nitrogen Nucleophiles • Organic Chemistry • organic chemistry functional groups • organic chemistry reactions • organic chemistry review • organic chemistry synthesis • organic method • organic reaction • organic reaction mechanism • Organic Syntheses • organic synthesis • organic synthesis reference work • Organische Chemie • Peptide synthesis • Practical • practical organic chemistry • reference work • Review • review organic synthesis • review synthetic methods • Sulfonamides • Sulfoximides • Suzuki reaction • Synthese • Synthetic chemistry • Synthetic Methods • Synthetic Organic Chemistry • synthetic transformation
• ISBN-10: 3-13-179081-4 / 3131790814
• ISBN-13: 978-3-13-179081-1 / 9783131790811