Organic Synthesis Using Transition Metals

About the Author xiii
Preface xv
1 Introduction 1
1.1 The Basics 2
1.2 The Basic Structural Types 2
1.3 Just How Many Ligands Can Fit around a Metal Atom? 10
1.4 Mechanism and the Basic Reaction Steps 13
1.5 Catalysis 17
References 19
2 Coupling Reactions 21
2.1 Carbon-Carbon Bond Formation 21
2.2 Lithium and Magnesium: Kumada Coupling 27
2.3 Zinc: The Negishi Reaction 32
2.4 Aluminium and Zirconium 35
2.5 Tin: The Stille Reaction 37
2.6 Boron: The Suzuki Reaction 46
2.7 Silicon: The Hiyama Reaction 57
2.8 Copper: The Sonogashira Reaction 61
2.9 Other Metals 67
2.10 Homocoupling 67
2.11 Enolate and Phenoxide Coupling 69
2.12 Heteroatom Coupling 70
References 82
3 C-H Activation 89
3.1 Arenes and Heteroarenes 91
3.2 Aldehydes 100
3.3 Borylation and Silylation 102
3.4 Allylic Functionalization 103
3.5 Unfunctionalized C-H Bonds 105
References 115
4 Carbonylation 117
4.1 Carbonylative Coupling Reactions: Synthesis of CarbonylDerivatives 117
4.2 Carbonylative Coupling Reactions: Synthesis of CarboxylicAcid Derivatives 122
4.3 Carbonylation of Alkenes and Alkynes 127
4.4 Hydroformylation 130
4.5 Stoichiometric Carbonylation Using Carbonyl Complexes139
4.6 Carboxylation 146
4.7 Decarbonylation and Decarboxylation 148
References 150
5 Alkene and Alkyne Insertion Reactions 153
5.1 The Heck Reaction 153
5.2 Insertion Reactions Involving Zirconium and Titanium 175
References 188
6 Electrophilic Alkene and Alkyne Complexes 191
6.1 Electrophilic Palladium Complexes 191
6.2 Other Metals: Silver, Gold, Platinum and Rare Earths 210
6.3 Iron 229
6.4 Cobaloxime _-Cations 235
References 237
7 Reactions of Alkyne Complexes 241
7.1 Alkyne Cobalt Complexes 241
7.2 Propargyl Cations: The Nicholas Reaction 244
7.3 The Pauson-Khand Reaction 246
7.4 Synthesis Using Multiple Cobalt Reactions 250
References 251
8 Carbene Complexes 253
8.1 Fischer Carbenes 253
8.2 Vinylidene Complexes 269
8.3 Metathesis Reactions Involving Carbene Complexes 273
8.4 Carbyne Complexes 310
8.5 Carbene Complexes from Diazo Compounds 312
References 319
9 eta3- or pi-Allyl Complexes325
9.1 Stoichiometric Reactions of pi-Allyl Complexes 325
9.2 Catalysis: Mostly Palladium 328
9.3 Propargyl Compounds 357
References 357
10 Diene, Dienyl and Arene Complexes 361
10.1 eta4-Diene Complexes 361
10.2 eta5-Dienyl Complexes 371
10.3 eta6-Arene Complexes 377
10.4 eta2-Arene Complexes 387
References 389
11 Cycloaddition and Cycloisomerization Reactions 391
11.1 Formal Six-Electron, Six-Atom Cycloadditions 391
11.2 Cycloadditions Involving Fewer than Six Atoms 402
11.3 Cycloadditions Involving More than Six Atoms 407
11.4 Isomerization 414
11.5 Cycloisomerization and Related Reactions 415
References 426
Abbreviations 431
Index of Principle Transition Metal Catalysts and Reagents433
Index 437