Catalyzed Carbon-Heteroatom Bond Formation

Catalyzed Carbon-Heteroatom Bond Formation......Page 1
Contents......Page 7
Preface......Page 15
List of Contributors......Page 17
1.2 Pd-Catalyzed Amination of Aryl Halides......Page 19
1.3 Synthesis of Saturated Nitrogen Heterocycles via Alkene, Alkyne, or Allene Aminopalladation Reactions......Page 21
1.3.1 PdII-Catalyzed Oxidative Amination of Alkenes......Page 22
1.3.2 Pd-Catalyzed Hydroamination Reactions of Alkenes and Alkynes......Page 24
1.3.3 Pd0-Catalyzed Carboamination Reactions of Alkenes......Page 26
1.3.5 Pd-Catalyzed Carboamination Reactions of Alkynes, Allenes, and Dienes......Page 28
1.3.6 Vicinal Difunctionalization of Alkenes and Allenes......Page 31
1.4.1 Reactions Involving Oxidative Addition of Allylic Electrophiles......Page 34
1.4.2 Reactions Involving π-Allylpalladium Intermediates Generated via Alkene Carbopalladation......Page 37
1.4.4 Generation of Allylpalladium Intermediates through C–H Activation......Page 39
1.5 Synthesis of Nitrogen Heterocycles via Pd-Catalyzed 1,3-Dipolar Cycloaddition Reactions......Page 40
1.6.1 Transformations Involving CO Insertion into Aryl or Alkenyl Pd-Carbon Bonds......Page 41
1.6.2 Transformations Involving CO Insertion Into a Pd–Heteroatom Bond......Page 43
1.6.3 Wacker-Type Carbonylative Processes......Page 44
References......Page 46
2.1 Introduction......Page 53
2.2.1 Carbonylation of C – X Bonds......Page 54
2.2.2 Carbonylation of C–M Bonds......Page 57
2.2.3 Hydrocarbonylation of C=C and C≡C Bonds......Page 58
2.2.4 Carbocarbonylation of C=C and C≡C Bonds......Page 60
2.2.5 Heterocarbonylation of C=C and C≡C Bonds......Page 61
2.2.6 Miscellaneous Lactone Syntheses Involving CO......Page 63
2.3.1 Hydrocarboxylation of C=C and C≡C Bonds......Page 64
2.3.2 Carbo- and Oxy-Carboxylation of C=C and C≡C Bonds......Page 68
2.4.1 Aldehyde Hydroacylation......Page 70
2.4.2 Ketone Hydroacylation......Page 71
2.4.3 [4 + 2] Annulation......Page 73
2.5.1 Oxidative Lactonization of Diols......Page 74
2.5.2 Reductive Cyclization of Ketoacids and Ketoesters......Page 75
2.5.3 C–H Oxygenation......Page 76
2.5.4 Ring Closure of Benzoic Acids with Dihaloalkanes......Page 77
2.5.6 Ring Opening of Cyclopropanes with Carboxylic Acids......Page 78
2.5.7 Ring Closure of o-Iodobenzoates with Aldehydes......Page 79
2.5.9 Michael Addition of α,β-Unsaturated N-Acylpyrrolidines......Page 80
2.5.11 Tandem Cross-Metathesis/Hydrogenation Route to Lactones......Page 81
2.5.12 Modern Catalytic Variants of Classical Macrolactonizations......Page 82
References......Page 83
3.1 Introduction......Page 87
3.2.1 Pd-Catalyzed Transformations......Page 88
3.2.2 Ni-Catalyzed Transformations......Page 95
3.2.3 Cu-Catalyzed Transformations......Page 97
3.2.4 Other Transition Metals as Catalysts......Page 106
3.3.1 Pd and Ni-Catalyzed Formation of Vinyl Chalcogenides......Page 108
3.3.2 Ni-Catalyzed Synthesis of Dienes......Page 118
3.3.3 Rh-Catalyzed Reactions......Page 119
3.3.4 Catalytic Addition of S-X and Se-X Bonds to Alkynes......Page 120
3.3.5 Catalytic Addition to Allenes......Page 121
3.4.1 Pd and Ni-Catalyzed Addition of Thiols and Selenols......Page 122
3.4.2 Rh and Pt-Catalyzed Addition of Thiols to Alkynes......Page 127
3.4.3 Catalytic Addition of Thiols and Selenols to Allenes......Page 129
3.5 Conclusions......Page 130
References......Page 131
4.1 Introduction......Page 137
4.2 Palladium-Catalyzed 1,2-Difunctionalization Reactions: Halogenation......Page 138
4.3 Aminohalogenation Reactions......Page 139
4.4 Dialkoxylation......Page 143
4.5 Aminoacetoxylation Reactions......Page 145
4.6 Diamination Reactions......Page 149
References......Page 152
5 Rhodium-Catalyzed C―H Aminations......Page 155
5.1 Metal Nitrenes from Iminoiodinanes......Page 157
5.1.1 Intramolecular C–H amination......Page 158
5.1.2 Intermolecular C–H Aminations......Page 162
5.1.3 Mechanism of C–H Amination using Hypervalent Iodine Reagents......Page 165
5.2 Metal Nitrenes from N-Tosyloxycarbamates......Page 167
References......Page 172
6.1 Introduction......Page 175
6.2.1 Addition to Alkynes......Page 177
6.2.2 Heteroatom Addition to Alkynes with Functionalization......Page 182
6.2.3 Heteroatom Addition to Allenes......Page 186
6.2.4 Heteroatom Additions to Alkenes......Page 189
6.3.1 Palladium-Catalyzed Carbon–Nitrogen Bond Formation......Page 192
6.3.2 Palladium-Catalyzed Carbon–Oxygen Bond Formation......Page 195
6.4 Palladium-Catalyzed Carbon–Heteroatom Bond Formation with Alkynes......Page 196
6.5 Heck Cyclizations......Page 200
6.6 Palladium Catalyzed C–H Bond Activation......Page 203
6.7 Multicomponent Coupling Reactions......Page 207
References......Page 212
7.1 Introduction......Page 217
7.2 Azide–Alkyne Cycloaddition: Basics......Page 218
7.3.1 Catalysts and Ligands......Page 221
7.3.3 Mechanistic aspects of the CuAAC Reaction......Page 226
7.3.5 Sulfonyl Triazoles as Stable Carbene Precursors......Page 233
7.3.6 Reactions of 1-Iodoalkynes......Page 236
7.3.7 Reactions of Copper Acetylides with Other Dipoles......Page 238
References......Page 239
8.1 Introduction......Page 245
8.2.1.1 Synthesis of Furans via Cycloisomerization Reactions......Page 246
8.2.1.2 Synthesis of Furans via "3 + 2" Cycloaddition Reactions......Page 282
8.2.2.1 Synthesis of Pyrroles via Cycloisomerization Reactions......Page 291
8.2.2.2 Synthesis of Pyrroles via "4 + 1" Cycloaddition Reactions......Page 301
8.2.2.3 Synthesis of Pyrroles via "3 + 2" Cycloaddition Reactions......Page 311
8.2.2.4 Synthesis of Pyrroles via "2 + 2 + 1" Cycloaddition Reactions......Page 316
8.3 Conclusion......Page 321
8.4 Abbreviations......Page 326
References......Page 327
9.1 Introduction......Page 335
9.2.1.1 Synthesis of Benzofurans via Cycloisomerization Reactions......Page 336
9.2.1.2 Synthesis of Benzofurans via Intramolecular Arylation Reactions......Page 345
9.2.1.3 Synthesis of Benzofurans via "4 + 1" Cycloaddition Reactions......Page 347
9.2.1.4 Synthesis of Benzofurans via "3 + 2" Cycloaddition Reactions......Page 349
9.2.2 Benzothiophenes......Page 351
9.2.2.1 Synthesis of Benzothiophenes via Cycloisomerization Reactions......Page 352
9.2.2.2 Synthesis of Benzothiophenes via "4 + 1" Cycloaddition Reactions......Page 355
9.2.2.3 Synthesis of Benzothiophenes via "3 + 2" Cycloaddition Reactions......Page 356
9.2.3 Indoles......Page 357
9.2.3.1 Synthesis of Indoles via Cycloisomerization Reactions......Page 358
9.2.3.2 Synthesis of Indoles via Intramolecular Arylation Reactions......Page 380
9.2.3.3 Synthesis of Indoles via "4 + 1" Cycloaddition Reactions......Page 386
9.2.3.4 Synthesis of Indoles via "3 + 2" Cycloaddition Reactions......Page 391
9.2.4.1 Synthesis of Isoindoles via Cycloisomerization Reactions......Page 399
9.2.5 Indolizines......Page 401
9.2.5.1 Synthesis of Indolizines via Cycloisomerization Reactions......Page 403
9.2.5.2 Synthesis of Indolizines via "3 + 2" Cycloaddition Reactions......Page 414
9.3 Conclusion......Page 417
9.4 Abbreviations......Page 419
References......Page 420
10.1 Introduction......Page 429
10.2 Ring-Opening meso-Oxabicyclic Alkenes with Oxygen-Based Nucleophiles......Page 430
10.3 Ring-Opening meso-Oxabicyclic Alkenes with Nitrogen-Based Nucleophiles......Page 435
10.4 Ring-Opening meso-Azabicyclic Alkenes with Nitrogen-Based Nucleophiles......Page 437
10.5 Ring-Opening meso-Oxabicyclic Alkenes with Sulfur-Based Nucleophiles......Page 441
10.6 Mechanistic Model......Page 442
10.7 Ring-Opening Unsymmetrical Oxa- and Aza-bicyclic Alkenes with Heteroatom Nucleophiles......Page 445
10.8 Ring-Opening of Vinyl Epoxides with Heteroatom Nucleophiles......Page 450
10.9 Conclusion......Page 452
References......Page 453
11.2.1.1 Intramolecular Processes......Page 455
11.2.1.2 Intermolecular Processes......Page 458
11.2.2 Acetylenic Schmidt Reaction......Page 459
11.2.3 Tandem C–N/C–C Bond Forming Processes......Page 460
11.2.4 Tandem C–N/C–X Bond Forming Processes......Page 464
11.3.1 Intramolecular Processes......Page 466
11.3.2 Intermolecular Processes......Page 467
11.3.3 Enantioselective Processes......Page 469
11.4.1.1 Sulfonamides as Nucleophiles......Page 471
11.4.1.2 Carboxamide Derivatives as Nucleophiles......Page 472
11.4.1.3 Ammonium Salts as Nucleophiles......Page 473
11.4.2 Methylenecyclopropanes, Vinylcyclopropanes, and Dienes......Page 474
11.5.1 Alkynes......Page 475
11.5.2 Allenes and Dienes......Page 476
References......Page 477
12.1 Introduction......Page 481
12.2.1.1 Intermolecular Processes......Page 482
12.2.1.2 Intramolecular Processes......Page 483
12.2.1.3 Tandem C–O/C–C Bond Forming Processes......Page 484
12.2.2 Ketones as Nucleophiles......Page 485
12.2.3 Aldehydes as Nucleophiles......Page 487
12.2.5.1 Acyl Migration Followed by Nucleophilc Attack......Page 489
12.2.5.2 Acyl Migration Followed by C=C/C≡C Addition......Page 491
12.2.5.3 Acyl Migration Leading to Diene/Ketone Formation......Page 492
12.2.6 Carbonates and Carbamates as Nucleophiles......Page 493
12.2.7 Ethers and Epoxides as Nucleophiles......Page 494
12.2.8 Additional Nucleophiles......Page 495
12.3.1.1 Intramolecular Processes......Page 496
12.3.1.2 Enantioselective Processes......Page 498
12.3.1.3 Intermolecular Processes......Page 500
12.3.2 Ketones as Nucleophiles......Page 501
12.3.3 Carboxylic Acid Derivatives as Nucleophiles......Page 502
12.4.1 Alkenes and Dienes......Page 503
12.4.2 Cyclization/Nucleophile Capture of Enynes......Page 505
References......Page 506
Index......Page 511