Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 4 (eBook)

Science of Synthesis – Volume 4: Compounds of Group 15 (As, Sb, Bi) and Silicon Compounds 1
Title page 3
Imprint 5
Preface 6
Volume Editor's Preface 7
Overview 10
Table of Contents 14
Introduction 48
4.1 Product Class 1: Arsenic Compounds 60
4.1.1 Product Subclass 1: Triorganoarsenic(III) and Related Compounds 60
Synthesis of Product Subclass 1 60
4.1.1.1 Method 1: Alkylation of Metallic Arsenides 60
4.1.1.2 Method 2: Transmetalation from Other Organometallic Reagents 61
4.1.1.2.1 Variation 1: From Grignard Reagents and Arsenic(III) Halides 61
4.1.1.2.2 Variation 2: From Organolithium Reagents and Arsenic(III) Halides 62
4.1.1.3 Method 3: Direct Synthesis from Metallic Arsenic 63
4.1.1.4 Method 4: Reduction of Arsenic(V) Oxides 63
4.1.1.5 Method 5: Addition of Arsines to Multiple Bonds 64
4.1.1.6 Method 6: Cleavage of Tetraorganoarsenic Derivatives 65
Applications of Product Subclass 1 in Organic Synthesis 65
4.1.1.7 Method 7: Triorganoarsenic(III) Derivatives as Halogen Equivalents 65
4.1.1.7.1 Variation 1: Nucleophilic Halovinylation 66
4.1.1.7.2 Variation 2: Carbonyl Haloalkenation 66
4.1.2 Product Subclass 2: Diorganoarsenic(III) and Related Compounds 66
Synthesis of Product Subclass 2 67
4.1.2.1 Method 1: Transmetalation from Other Organometallic Reagents 67
4.1.2.1.1 Variation 1: From Grignard Reagents and Arsenic(III) Halides 67
4.1.2.1.2 Variation 2: From Organolithium Reagents and Arsenic(III) Halides 67
4.1.2.2 Method 2: Synthesis from Elemental Arsenic 68
4.1.2.3 Method 3: Thermolysis of Arsenic(V) Derivatives 68
4.1.2.4 Method 4: Redistribution Reactions 69
4.1.3 Product Subclass 3: Monoorganoarsenic(III) and Related Compounds 69
Synthesis of Product Subclass 3 70
4.1.3.1 Method 1: Transmetalation from Other Organometallic Reagents 70
4.1.3.1.1 Variation 1: From Grignard Reagents and Arsenic(III) Derivatives 70
4.1.3.1.2 Variation 2: From Organolithium Reagents and Arsenic(III) Derivatives 70
4.1.3.2 Method 2: Reduction of Arsonic Acids 71
4.1.3.3 Method 3: Redistribution Reactions 71
4.1.4 Product Subclass 4: Pentaorganoarsenic(V) and Related Compounds 72
Synthesis of Product Subclass 4 72
4.1.4.1 Method 1: Transmetalation from Other Organometallic Reagents 72
4.1.4.2 Method 2: Reaction Of Arsinimines with Organolithium Reagents 73
4.1.5 Product Subclass 5: Arsonium Ylides and Related Compounds 73
Synthesis of Product Subclass 5 73
4.1.5.1 Method 1: From Arsonium Salts by the “Salt Method” 74
4.1.5.2 Method 2: From Reaction with Arsenic(V) Dihalides 74
4.1.5.3 Method 3: From Arsine Oxides 75
4.1.5.4 Method 4: From Diazonium Salts 75
4.1.5.5 Method 5: From Other Ylides by “Transylidation” 76
Applications of Product Subclass 5 in Organic Synthesis 77
4.1.5.6 Method 6: Reactions of Stabilized Arsonium Ylides with Nonconjugated Carbonyl Compounds 77
4.1.5.6.1 Variation 1: Reactions of Stabilized Arsonium Ylides with a,ß-Unsaturated Carbonyl Compounds 79
4.1.5.7 Method 7: Reactions of Semistabilized Arsonium Ylides with Carbonyl Compounds 79
4.1.5.8 Method 8: Reactions of Reactive Arsonium Ylides with Carbonyl Compounds 83
4.1.6 Product Subclass 6: Tetraorganoarsenic(V) and Related Compounds 84
Synthesis of Product Subclass 6 84
4.1.6.1 Method 1: By Alkylation of Organoarsenic(III) Derivatives 84
4.1.6.2 Method 2: Reaction of Arsine Oxides with Grignard Reagents 85
4.1.7 Product Subclass 7: Triorganoarsenic(V) and Related Compounds 85
Synthesis of Product Subclass 7 85
4.1.7.1 Method 1: Oxidation of Triorganoarsenic(III) Compounds 85
4.1.7.1.1 Variation 1: Reaction With Halogens 86
4.1.7.1.2 Variation 2: Reaction with “Halogen Substitute” Compounds 86
4.1.7.1.3 Variation 3: Reaction with Active Oxygen Compounds 87
Applications of Product Subclass 7 in Organic Synthesis 88
4.1.7.2 Method 2: Triorganoarsenic(V) Derivatives as Halogen Equivalents 88
4.1.8 Product Subclass 8: Diorganoarsenic(V) and Related Compounds 88
Synthesis of Product Subclass 8 89
4.1.8.1 Method 1: From Diazonium Salts: The Bart Reaction 89
4.1.8.2 Method 2: From Alkaline Alkyl Arsonate Salts: The Meyer Reaction 89
4.1.9 Product Subclass 9: Monoorganoarsenic(V) and Related Compounds 90
Synthesis of Product Subclass 9 90
4.1.9.1 Method 1: The Bart Reaction 90
4.1.9.1.1 Variation 1: The Scheller Modification of the Bart Reaction 91
4.1.9.2 Method 2: The Béchamp Reaction 92
4.1.9.3 Method 3: The Meyer Reaction 92
4.1.9.3.1 Variation 1: The Rosenmund Reaction 93
4.1.9.4 Method 4: Oxidative Hydrolysis 93
4.2 Product Class 2: Antimony Compounds 100
4.2.1 Product Subclass 1: Tertiary Stibines 100
Synthesis of Product Subclass 1 100
4.2.1.1 Method 1: From Alkali Metal Antimonides 100
4.2.1.1.1 Variation 1: Cleavage of an Aryl--Antimony Bond 101
4.2.1.1.2 Variation 2: Cleavage of an Alkyl--Antimony Bond 101
4.2.1.1.3 Variation 3: Cleavage of a Halo--Antimony Bond 102
4.2.1.2 Method 2: By Transmetalation 102
4.2.1.2.1 Variation 1: Formation of Symmetrical Tertiary Stibines Using Grignard Reagents 102
4.2.1.2.2 Variation 2: Formation of Nonsymmetrical Tertiary Stibines Using Organolithiums 103
Applications of Product Subclass 1 in Organic Synthesis 104
4.2.1.3 Method 3: Alkenation Reactions 104
4.2.1.3.1 Variation 1: Wittig-type Alkenation of Aldehydes Mediated by Tributylstibine 104
4.2.1.3.2 Variation 2: Alkenation of Aldehydes with Dibromomalonates 104
4.2.1.4 Method 4: Palladium-Catalyzed Processes 105
4.2.2 Product Subclass 2: Di- and Monoorganostibines 105
Synthesis of Product Subclass 2 105
4.2.2.1 Method 1: By Cleavage of Distibines 106
4.2.2.2 Method 2: By Redistribution Reactions 106
4.2.2.2.1 Variation 1: Reaction of Antimony(III) Halides with Triarylstibines 106
4.2.2.2.2 Variation 2: Reaction of Antimony(III) Halides with Halostibines 107
4.2.2.3 Method 3: By Transmetalation 107
4.2.2.3.1 Variation 1: From Tetraalkyllead 107
4.2.2.3.2 Variation 2: From Organostannanes 108
4.2.2.4 Method 4: From .5-Stibanes 108
4.2.2.4.1 Variation 1: Thermolysis of Dihalotriorgano-.5-stibanes 108
4.2.2.4.2 Variation 2: Thermolysis of Trihalodiorgano-.5-stibanes 109
4.2.2.4.3 Variation 3: Reduction of .5-Stibanes 109
4.2.3 Product Subclass 3: Pentaorgano-.5-stibanes 109
Synthesis of Product Subclass 3 109
4.2.3.1 Method 1: Synthesis of Symmetrical Pentaorgano-.5-stibanes 110
4.2.3.2 Method 2: Synthesis of Unsymmetrical Pentaorgano-.5-stibanes 110
Applications of Product Subclass 3 in Organic Synthesis 110
4.2.3.3 Method 3: Reaction of .5-Stibanes with Electrophiles 110
4.2.4 Product Subclass 4: Stibonium Ylides and Stibimines 111
Synthesis of Product Subclass 4 111
4.2.4.1 Method 1: Use of Diazo Compounds 111
4.2.4.2 Method 2: From Sulfonyl Azides 112
Applications of Product Subclass 4 in Organic Synthesis 112
4.2.4.3 Method 3: Wittig-type Reactions of Stibonium Ylides 112
4.2.5 Product Subclass 5: Tetraorgano-.5-stibanes 113
Synthesis of Product Subclass 5 113
4.2.5.1 Method 1: By Cleavage of Pentaorgano-.5-stibanes 113
4.2.5.2 Method 2: From Tertiary Stibines 113
4.2.5.2.1 Variation 1: By Alkylation of Trialkylstibines 113
4.2.5.2.2 Variation 2: By Arylation of Triarylstibines 114
Applications of Product Subclass 5 in Organic Synthesis 114
4.2.5.3 Method 3: Allylation of Aldehydes by .5-Stibanes 114
4.2.6 Product Subclass 6: Triorgano-.5-stibanes 115
Synthesis of Product Subclass 6 115
4.2.6.1 Method 1: Oxidation of Tertiary Stibines with Bromine 115
Applications of Product Subclass 6 in Organic Synthesis 115
4.2.6.2 Method 2: Formation of Diketones 115
4.2.7 Product Subclass 7: Di- and Monoorgano-.5-stibanes 116
Synthesis of Product Subclass 7 116
4.2.7.1 Method 1: By Transmetalation 116
4.2.7.2 Method 2: From Tertiary Stibines 117
4.2.7.2.1 Variation 1: Cleavage of Triphenylstibine 117
4.2.7.2.2 Variation 2: Halogenation of Halodiorganostibines 117
4.2.7.3 Method 3: From Diazonium Salts 117
4.2.7.3.1 Variation 1: Preparation of Unsymmetrical Hydroxystibine Oxides 117
4.2.7.3.2 Variation 2: Preparation of Dihydroxystibine Oxides by the Scheller Reaction 118
4.3 Product Class 3: Bismuth Compounds 124
Synthesis of Product Class 3 124
4.3.1 Product Subclass 1: Alkyl- and Arylbismuthines 124
4.3.1.1 Method 1: From Grignard and Organolithium Reagents 125
4.3.1.2 Method 2: From Alkali Bismuthides 128
4.3.1.3 Method 3: By Transmetalation 128
4.3.1.4 Additional Methods 129
4.3.2 Product Subclass 2: Alkyl- and Arylhalobismuthines 130
4.3.2.1 Method 1: By Bi--C Bond Cleavage and Redistribution Reactions 131
4.3.2.2 Method 2: From Organometallic Reagents 133
4.3.3 Product Subclass 3: Alkyl- and Arylbismuthines Containing Bonds between Bismuth and Group 15 or 16 Elements 134
4.3.3.1 Method 1: From Halobismuthines 135
4.3.3.2 Method 2: From Alkoxybismuthines 136
4.3.3.3 Method 3: By Cleavage of Bi--C Bond(s) by Acidic Compounds 136
4.3.3.4 Additional Methods 137
4.3.4 Product Subclass 4: Dibismuthines and Dibismuthenes 138
4.3.4.1 Method 1: From Tertiary Bismuthines 140
4.3.4.2 Method 2: From Halodiorganobismuthines 140
4.3.5 Product Subclass 5: Organobismuth Compounds with Bismuth--Transition Metal Bonds 141
4.3.6 Product Subclass 6: Alkoxy- and Hydroxybismuthine Oxides 141
4.3.7 Product Subclass 7: Dihalotriorganobismuth(V) and Related Compounds 142
4.3.7.1 Method 1: Oxidative Addition of Halogen or Halogen Equivalent to Triorganobismuthines 143
4.3.7.2 Method 2: Oxidation of Bismuthines with Ozone, Peroxy Acids, and Other Oxygen Equivalents 144
4.3.7.3 Method 3: By Metathetical Reactions 144
4.3.8 Product Subclass 8: Oxybis[triarylhalobismuth(V)] and Related Compounds 145
4.3.9 Product Subclass 9: Bismuthine Imides 146
4.3.9.1 Method 1: From Tertiary Bismuthines 146
4.3.9.2 Method 2: From Triaryldihalobismuth(V) 147
4.3.10 Product Subclass 10: Bismuthine Oxides 147
4.3.11 Product Subclass 11: Bismuthonium Salts 149
4.3.11.1 Method 1: From Pentaarylbismuth(V) Compounds 150
4.3.11.2 Method 2: From Triaryldifluorobismuth(V) 151
4.3.11.3 Method 3: From Tertiary Bismuthines 152
4.3.12 Product Subclass 12: Bismuthonium Ylides 152
4.3.12.1 Method 1: From Tertiary Bismuthines 152
4.3.12.2 Method 2: From Triarylbismuth(V) Compounds 153
4.3.12.3 Method 3: From Bismuthonium Salts 154
4.3.13 Product Subclass 13: Pentaorganobismuth(V) Compounds 154
4.3.14 Product Subclass 14: Hexaorganobismuthates 155
Applications of Product Class 3 in Organic Synthesis 155
4.4 Product Class 4: Silicon Compounds 164
4.4.1 Product Subclass 1: Disilenes 164
Synthesis of Product Subclass 1 166
4.4.1.1 Method 1: Photolysis of Linear Trisilanes 166
4.4.1.2 Method 2: Photolysis of Cyclotrisilanes 167
4.4.1.3 Method 3: Reductive Coupling of Dihalosilanes 168
4.4.1.4 Method 4: Reduction of 1,2-Dihalodisilanes 169
4.4.1.5 Method 5: Photolysis of 2,3-Disilabicyclo[2.2.2]octa-5,7-dienes 170
4.4.1.6 Additional Methods 170
4.4.2 Product Subclass 2: Silenes 172
Synthesis of Product Subclass 2 174
4.4.2.1 Method 1: By Photolysis or Thermolysis of Acylsilanes 174
4.4.2.1.1 Variation 1: Photolysis of Acylsilanes 174
4.4.2.1.2 Variation 2: Thermolysis of Acylpolysilanes 175
4.4.2.2 Method 2: By 1,2-Salt Elimination from a-Lithiated Silanes 175
4.4.2.2.1 Variation 1: By Metalation of the Ca--H Bond of Alkylsilanes 176
4.4.2.2.2 Variation 2: By Metalation of the C--Br Bond of a-Bromoalkylsilanes 177
4.4.2.2.3 Variation 3: From Halo(vinyl)silanes 177
4.4.2.3 Method 3: Sila-Peterson Reactions 178
4.4.2.3.1 Variation 1: From the Addition of Silyl Anions to Ketones 178
4.4.2.3.2 Variation 2: From the Addition of Organolithium Reagents to Acylpolysilanes 179
4.4.2.3.3 Variation 3: By the Deprotonation of a-Hydroxysilanes 179
4.4.2.4 Additional Methods 180
4.4.3 Product Subclass 3: Silylenes 182
Synthesis of Product Subclass 3 184
4.4.3.1 Method 1: Reduction of Dihalosilanes 184
Applications of Product Subclass 3 in Organic Synthesis 188
4.4.3.2 Method 2: Insertion Reactions 188
4.4.3.3 Method 3: Addition Reactions 194
4.4.3.3.1 Variation 1: To Dienes 194
4.4.3.3.2 Variation 2: To Aldehydes, Ketones, and Imines 195
4.4.3.3.3 Variation 3: To Alkynes and Nitriles 199
4.4.3.3.4 Variation 4: To Isocyanides and Azides 199
4.4.3.3.5 Variation 5: To Transition Metals 200
4.4.4 Product Subclass 4: Silyl Hydrides 206
Synthesis of Product Subclass 4 207
4.4.4.1 Method 1: From Inorganic Silanes 207
4.4.4.2 Method 2: From Aryl- and Alkylsilyl Hydrides 210
4.4.4.3 Method 3: From Silyl Halides 215
4.4.4.4 Method 4: From Silyl Ethers 217
4.4.4.5 Methods 5: Additional Methods 218
Applications of Product Subclass 4 in Organic Synthesis 219
4.4.4.6 Method 6: Hydrosilylation of Alkenes, Alkynes, and Related Compounds 219
4.4.4.7 Method 7: Silyl Hydrides as Reducing Reagents 223
4.4.5 Product Subclass 5: Disilanes 234
Synthesis of Product Subclass 5 235
4.4.5.1 Method 1: Via Coupling of Hydrosilanes 235
4.4.5.1.1 Variation 1: By Use of Transition Metal Catalysts 235
4.4.5.1.2 Variation 2: By Photolysis of Alkylhydrosilanes in the Presence of Mercury 236
4.4.5.2 Method 2: Via Photolysis of Organopolysilanes in the Presence of Hydrosilanes 237
4.4.5.3 Method 3: Via Coupling of (Organosilyl)alkali Metal Salts with Halosilanes 237
4.4.5.4 Method 4: Via Coupling of Halosilanes Using Metals or Metal Salts 238
4.4.5.4.1 Variation 1: By Use of Alkali Metals 239
4.4.5.4.2 Variation 2: By Use of Magnesium Metal 239
4.4.5.4.3 Variation 3: By Use of Lithium Naphthalenide 240
4.4.5.4.4 Variation 4: By Use of Samarium(II) Iodide 241
4.4.5.4.5 Variation 5: By Use of Potassium--Graphite Laminate (C8K) 241
4.4.5.5 Method 5: Via Electrochemical Reduction of Halosilanes 242
4.4.5.6 Method 6: Via Photolysis of Organopolysilanes in the Presence of Trapping Agents 243
4.4.5.6.1 Variation 1: In the Presence of Ketones 243
4.4.5.6.2 Variation 2: In the Presence of Functionalized Alkenes 244
4.4.5.7 Method 7: From Halodisilanes and Organometallic Reagents 245
4.4.5.8 Additional Methods 245
Applications of Product Subclass 5 in Organic Synthesis 246
4.4.6 Product Subclass 6: Silyltin Reagents 252
Synthesis of Product Subclass 6 252
4.4.6.1 Method 1: Synthesis of Silyltin Reagents 252
Applications of Product Subclass 6 in Organic Synthesis 254
4.4.7 Product Subclass 7: Silylboron Reagents 258
Synthesis of Product Subclass 7 258
4.4.7.1 Method 1: Synthesis of Silylboron Reagents 258
4.4.7.1.1 Variation 1: Synthesis of (Dimethylphenylsilyl)(pinacol)borane from Dimethylphenylsilyllithium and Pinacolborane 260
4.4.7.1.2 Variation 2: Synthesis of (Dimethylphenylsilyl)(pinacol)borane from Dimethylphenylsilyllithium and Isopropoxy(pinacol)borane 261
4.4.7.1.3 Variation 3: Synthesis of Lithium Triethyl(dimethylphenylsilyl)borate 261
Applications of Product Subclass 7 in Organic Synthesis 262
4.4.8 Product Subclass 8: Silylaluminum Reagents 266
Synthesis of Product Subclass 8 266
4.4.8.1 Method 1: Tris(trimethylsilyl)aluminum from Bis(trimethylsilyl)mercury(II) 266
4.4.8.1.1 Variation 1: Tris(trimethylsilyl)aluminum from Chlorotrimethylsilane and Aluminum, Lithium, and Mercury Metals 267
4.4.8.2 Additional Methods 268
Applications of Product Subclass 8 in Organic Synthesis 268
4.4.9 Product Subclass 9: Silylzinc Reagents 272
Synthesis of Product Subclass 9 272
4.4.9.1 Method 1: From a Triorganosilyl Anion Source and Zinc(II) Reagents 272
4.4.9.1.1 Variation 1: Dialkyl(triorganosilyl)zincate Reagents from an Alkylmetal, Triorganosilylmetal Reagents, and Zinc(II) Salts 274
Applications of Product Subclass 9 in Organic Synthesis 274
4.4.10 Product Subclass 10: Silylcopper Reagents 278
Synthesis of Product Subclass 10 278
4.4.10.1 Method 1: Synthesis of Triorganosilylcopper(I) Reagents 278
4.4.10.2 Method 2: Synthesis of Mixed Alkyl(triorganosilyl)copper(I) Reagents 279
Applications of Product Subclass 10 in Organic Synthesis 280
4.4.11 Product Subclass 11: Silyllithium Reagents 284
Synthesis of Product Subclass 11 285
4.4.11.1 Method 1: By Lithiation of Halotriorganosilanes 285
4.4.11.1.1 Variation 1: Using Lithium Metal 285
4.4.11.1.2 Variation 2: Using an Alkyllithium Reagent 286
4.4.11.2 Method 2: Via Si--Si Bond Cleavage 286
4.4.11.2.1 Variation 1: Reductive Cleavage Using Lithium Metal 287
4.4.11.2.2 Variation 2: Nucleophilic Cleavage Using an Alkyllithium Reagent 287
4.4.11.3 Method 3: Via Si--Sn Bond Cleavage 288
4.4.11.4 Method 4: From Bis(triorganosilyl)mercury(II) Compounds 289
Applications of Product Subclass 11 in Organic Synthesis 289
4.4.12 Product Subclass 12: Haloorganosilanes 294
Synthesis of Product Subclass 12 296
4.4.12.1 Method 1: Conversion of Hydridoorganosilanes into Haloorganosilanes 296
4.4.12.1.1 Variation 1: By Reaction with Copper(II) Halides 296
4.4.12.1.2 Variation 2: By Reaction with Hydrogen Halides, Haloalkanes, or Haloarenes 297
4.4.12.1.3 Variation 3: By Reaction with Reactive Organic Halides in the Presence of Tertiary Amines 298
4.4.12.1.4 Variation 4: By Reaction with Dihalogens 299
4.4.12.2 Method 2: Halogenolysis of Disilanes 299
4.4.12.3 Method 3: Halogenolysis of Si--C Bonds 299
4.4.12.4 Method 4: Halogen Exchange 301
4.4.12.4.1 Variation 1: Generation In Situ 302
4.4.12.5 Method 5: Conversion of Disiloxanes into Haloorganosilanes 302
4.4.12.6 Method 6: Direct Synthesis from Silicon and Organic Halides 303
4.4.12.7 Method 7: Hydrosilylation of Unsaturated Bonds with Halohydridosilanes 304
4.4.12.8 Method 8: Organometallic Exchange of Halogen in a Halosilane To Give a New Halosilane 305
Applications of Product Subclass 12 in Organic Synthesis 307
4.4.12.9 Fluoroorganosilanes 307
4.4.12.10 Chloroorganosilanes 308
4.4.12.11 Bromoorganosilanes 309
4.4.12.12 Iodoorganosilanes 310
4.4.13 Product Subclass 13: Silyl Diethers 316
Synthesis of Product Subclass 13 316
4.4.13.1 Method 1: Synthesis of Symmetrical Acyclic Silyl Diethers 316
4.4.13.1.1 Variation 1: From Silanes 317
4.4.13.1.2 Variation 2: From Dichlorosilanes 318
4.4.13.2 Method 2: Synthesis of Unsymmetrical Acyclic Silyl Diethers 320
4.4.13.2.1 Variation 1: From Alkoxy(halo)silanes 320
4.4.13.2.2 Variation 2: From Chlorosilyl Pent-4-enyl Ethers 323
4.4.13.3 Method 3: Synthesis of Cyclic Silyl Diethers 324
4.4.13.3.1 Variation 1: From Silanes 324
4.4.13.3.2 Variation 2: From Dichlorosilanes or Silyl Trifluoromethanesulfonates 325
4.4.13.3.3 Variation 3: From Hexamethylcyclotrisilazane 327
Applications of Product Subclass 13 in Organic Synthesis 328
4.4.13.4 Method 4: Intramolecular Reactions Using Silicon-Tethered Reactants 328
4.4.13.5 Method 5: Standard Protection of Alcohols 335
4.4.14 Product Subclass 14: Silyl Esters 340
Synthesis of Product Subclass 14 342
4.4.14.1 Silyl Sulfates and Trifluoromethanesulfonates 342
4.4.14.1.1 Method 1: Polymer-Supported Silyl Trifluoromethanesulfonates 342
4.4.14.1.2 Method 2: Reaction of Tetrasubstituted Silanes with Trifluoromethanesulfonic Acid 342
4.4.14.1.2.1 Variation 1: Using Trisubstituted Allylsilanes 343
4.4.14.1.3 Method 3: Reaction of Trialkylchlorosilanes with Trifluoromethanesulfonic Acid 343
4.4.14.1.4 Method 4: Reaction of Trialkylchlorosilanes with Sulfuric Acid 344
4.4.14.2 Silyl Phosphates 344
4.4.14.2.1 Method 1: Reaction of Bis(trimethylsilyl) Ether with Phosphorus Pentoxide 344
4.4.14.3 Silyl Carboxylates 345
4.4.14.3.1 Method 1: Reaction of Hydrosilanes with Carboxylic Acids 345
4.4.14.3.2 Method 2: Reaction of Trialkylchlorosilanes with Carboxylic Acids 346
4.4.14.3.2.1 Variation 1: With Sterically Hindered Trialkylchlorosilanes 347
4.4.14.3.3 Method 3: Reaction of Carboxylic Acids with Trialkylsilyl Trifluoromethanesulfonates 347
4.4.14.3.3.1 Variation 1: With Trialkylsilyl Trifluoromethanesulfonates Formed In Situ 348
4.4.14.3.4 Method 4: Reaction of Carboxylic Acids with N,N'-Bis(trimethylsilyl)urea 349
4.4.14.4 Additional Methods 349
4.4.15 Product Subclass 15: Silyl Imidic Esters (Silylimino Ethers) 352
Synthesis of Product Subclass 15 353
4.4.15.1 Method 1: Silylation of Amide Derivatives 353
4.4.15.1.1 Variation 1: With Chlorosilanes 353
4.4.15.1.2 Variation 2: With Silyl Triflates 354
4.4.15.1.3 Variation 3: With Trimethylsilyldimethylamine 355
4.4.15.1.4 Variation 4: With Hexamethyldisilazane 355
4.4.15.1.5 Variation 5: Silylamide-Based Silylation 356
4.4.15.2 Method 2: Catalytic Silylation with Trimethyl(pentafluorophenyl)silane 357
4.4.15.3 Method 3: Coupling of Alkali Metal Hexamethyldisilazanides with Acid Derivatives 358
4.4.15.3.1 Variation 1: With Acyl Chlorides 358
4.4.15.3.2 Variation 2: With Esters 359
4.4.15.4 Method 4: Acylation of Trimethylsilylhydroxylamines and Bis(trimethylsilyl)carbodiimide 359
4.4.15.4.1 Variation 1: With Acyl Chlorides 359
4.4.15.4.2 Variation 2: With Ketenes 360
4.4.15.5 Method 5: Insertion of Formaldehyde into the Si--N Bond of O,N-Bis(silyl)amides 361
4.4.15.6 Additional Methods 361
4.4.16 Product Subclass 16: Silyl Enol Ethers 364
Synthesis of Product Subclass 16 377
4.4.16.1 Method 1: From Carbonyl Compounds, Bases, and Electrophilic Silylating Agents 377
4.4.16.1.1 Variation 1: Synthesis of Silyl Enol Ethers of Aldehydes and Ketones 378
4.4.16.1.2 Variation 2: Synthesis of Silyl Ketene Acetals and Related Compounds 383
4.4.16.1.3 Variation 3: Synthesis of Siloxybutadienes 388
4.4.16.1.4 Variation 4: Chemoselective Synthesis of Silyl Enol Ethers 390
4.4.16.1.5 Variation 5: Enantioselective Synthesis of Silyl Enol Ethers 391
4.4.16.1.6 Variation 6: Synthesis of Polymer-Supported Silyl Enol Ethers 392
4.4.16.2 Method 2: From a,ß-Unsaturated Carbonyl Compounds by Reductive Silylation 393
4.4.16.2.1 Variation 1: By Metal Reduction and Subsequent Enolate Trapping 393
4.4.16.2.2 Variation 2: By Conjugate Addition of Nucleophiles and Subsequent Enolate Trapping 394
4.4.16.2.3 Variation 3: By Hydrosilylation 396
4.4.16.3 Method 3: From Diesters in the Acyloin Condensation 397
4.4.16.4 Method 4: From a-Halo Carbonyl Compounds by Reductive Silylation 397
4.4.16.5 Method 5: From Alkenes by Hydrosilylation in the Presence of Carbon Monoxide 398
4.4.16.6 Method 6: From Acylsilanes by Nucleophilic Addition and Brook Rearrangement 399
4.4.16.6.1 Variation 1: With Alkenyl- or Alkynylmetals 399
4.4.16.6.2 Variation 2: With Nucleophilic Reagents Having an a-Leaving Group 400
4.4.16.7 Method 7: From Silyl Esters by Alkylidenation 401
4.4.16.8 Method 8: Rearrangements of Silyl Ethers 402
4.4.16.8.1 Variation 1: Via Rearrangement of ß-Siloxy Carbenoids 402
4.4.16.8.2 Variation 2: Via Isomerization of Allyl and Propargyl Silyl Ethers 402
4.4.16.8.3 Variation 3: Via Rearrangement of Silyl Cyclopropyl Ethers 403
4.4.16.9 Method 9: By Oxidation of Vinyllithiums 404
4.4.16.10 Method 10: From Ketenes by Haloalkylsilane Trapping of Lithium Enolates 404
4.4.16.11 Method 11: Interconversion of Silyl Enol Ethers 405
4.4.16.11.1 Variation 1: Introduction of Nitrogen-Based Functional Groups at the a-Position 405
4.4.16.11.2 Variation 2: Introduction of Nitrogen-Based Functional Groups at the ß-Position 405
4.4.16.11.3 Variation 3: Ene-like Reactions of Silyl Enol Ethers with Aldehydes 406
4.4.16.11.4 Variation 4: Alkylation and Arylation of 2-Siloxyallyl Halides 407
4.4.16.11.5 Variation 5: Isomerization of Silyl Enol Ethers 407
4.4.16.11.6 Variation 6: Conversion of Trimethylsilyl Enol Ethers into Trichlorosilyl Enol Ethers 408
4.4.16.12 Additional Methods 408
4.4.17 Product Subclass 17: Silyl Ethers 418
4.4.17.1 Trimethylsilyl Ethers 419
Formation 419
4.4.17.1.1 Method 1: Silylation of Alcohols with Chlorotrimethylsilane 419
4.4.17.1.2 Method 2: Silylation of Alcohols with Trimethylsilyl Trifluoromethanesulfonate 420
4.4.17.1.3 Method 3: Silylation of Alcohols with Trimethylsilyl Cyanide 420
4.4.17.1.4 Method 4: Silylation of Alcohols with N,O-Bis(trimethylsilyl)acetamide 421
Cleavage 422
4.4.17.1.5 Method 5: Cleavage of Trimethylsilyl Ethers with Acidic Reagents 422
4.4.17.1.6 Method 6: Cleavage of Trimethylsilyl Ethers under Basic Conditions 423
4.4.17.2 Triethylsilyl Ethers 424
Formation 424
4.4.17.2.1 Method 1: Silylation of Alcohols with Chlorotriethylsilane 424
4.4.17.2.1.1 Variation 1: With Chlorotriethylsilane in Pyridine 425
4.4.17.2.1.2 Variation 2: With Chlorotriethylsilane in the Presence of 4-(Dimethylamino)pyridine 426
4.4.17.2.2 Method 2: Silylation of Alcohols with Triethylsilyl Trifluoromethanesulfonate 427
Cleavage 427
4.4.17.2.3 Method 3: Cleavage of Triethylsilyl Ethers under Acidic Conditions 427
4.4.17.2.3.1 Variation 1: In the Presence of 4-Toluenesulfonic Acid 428
4.4.17.2.3.2 Variation 2: With Trifluoromethanesulfonic Acid 429
4.4.17.2.4 Method 4: Cleavage of Triethylsilyl Ethers with Tetrabutylammonium Fluoride 429
4.4.17.3 tert-Butyldimethylsilyl Ethers 430
Formation 430
4.4.17.3.1 Method 1: Silylation of Alcohols with tert-Butyldimethylsilyl Chloride 430
4.4.17.3.1.1 Variation 1: In the Presence of 4-(Dimethylamino)pyridine 431
4.4.17.3.1.2 Variation 2: In Dichloromethane 431
4.4.17.3.2 Method 2: Silylation of Alcohols with tert-Butyldimethylsilyl Trifluoromethanesulfonate 432
4.4.17.3.2.1 Variation 1: Selective Silylation of Phenols 433
4.4.17.3.2.2 Variation 2: Selective Silylation of Alcohols 433
4.4.17.3.3 Method 3: Migration of a tert-Butyldimethylsilyl Group from a tert-Butyldimethylsilyl Ether to an Alcohol 434
Cleavage 435
4.4.17.3.4 Method 4: Cleavage of tert-Butyldimethylsilyl Ethers with Tetrabutylammonium Fluoride 435
4.4.17.3.5 Method 5: Cleavage of tert-Butyldimethylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride 437
4.4.17.3.6 Method 6: Cleavage of tert-Butyldimethylsilyl Ethers under Acidic Conditions 438
4.4.17.3.6.1 Variation 1: With Hydrogen Fluoride--Pyridine Complex 438
4.4.17.3.6.2 Variation 2: With Mineral Acid 439
4.4.17.3.6.3 Variation 3: With Organic Acids 440
4.4.17.3.6.4 Variation 4: With Lewis Acids 442
4.4.17.4 Triisopropylsilyl Ethers 443
Formation 443
4.4.17.4.1 Method 1: Silylation of Alcohols with Triisopropylsilyl Trifluoromethanesulfonate and 2,6-Lutidine 443
4.4.17.4.1.1 Variation 1: With Triisopropylsilyl Trifluoromethanesulfonate in the Presence of 4-(Dimethylamino)pyridine 444
Cleavage 444
4.4.17.4.2 Method 2: Cleavage of Triisopropylsilyl Ethers with Tetrabutylammonium Fluoride 444
4.4.17.4.3 Method 3: Cleavage of Triisopropylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride 445
4.4.17.4.4 Method 4: Cleavage of Triisopropylsilyl Ethers with Hydrogen Fluoride--Pyridine Complex 446
4.4.17.4.5 Method 5: Cleavage of Triisopropylsilyl Ethers under Acidic Conditions 447
4.4.17.5 tert-Butyldiphenylsilyl Ethers 448
Formation 448
4.4.17.5.1 Method 1: Silylation of Alcohols with tert-Butyldiphenylsilyl Chloride 448
4.4.17.5.1.1 Variation 1: In the Presence of 4-(Dimethylamino)pyridine 449
4.4.17.5.1.2 Variation 2: Using Butyllithium 449
4.4.17.5.2 Method 2: Silylation of Alcohols with tert-Butyldiphenylsilyl Trifluoromethanesulfonate 450
4.4.17.5.3 Method 3: Migration of a tert-Butyldiphenylsilyl Group to an Alcohol 450
Cleavage 451
4.4.17.5.4 Method 4: Cleavage of tert-Butyldiphenylsilyl Ethers with Tetrabutylammonium Fluoride 451
4.4.17.5.5 Method 5: Cleavage of tert-Butyldiphenylsilyl Ethers with Tetrabutylammonium Fluoride in Acetic Acid 453
4.4.17.5.6 Method 6: Cleavage of tert-Butyldiphenylsilyl Ethers with Tris(dimethylamino)sulfur (Trimethylsilyl)difluoride 453
4.4.17.5.7 Method 7: Cleavage of tert-Butyldiphenylsilyl Ethers with Hydrogen Fluoride--Pyridine Complex 454
4.4.17.5.7.1 Variation 1: Cleavage with Hydrogen Fluoride--Triethylamine Complex 455
4.4.17.6 Other Silyl Ethers 456
4.4.18 Product Subclass 18: Silyl Peroxides 460
Synthesis of Product Subclass 18 460
4.4.18.1 Method 1: Synthesis of Silyl Peroxides 460
Applications of Product Subclass 18 in Organic Synthesis 461
4.4.18.2 Method 2: Various Oxidations Using Silyl Peroxides 461
4.4.18.3 Method 3: Synthesis of Alcohols via Silyl Peroxides 463
4.4.18.3.1 Variation 1: Oxidation of Heteroatom-Substituted Organosilicon Compounds 463
4.4.18.3.2 Variation 2: Oxidation of Phenyl-Substituted Organosilicon Compounds 465
4.4.18.3.3 Variation 3: Oxidation of Heteroaromatic-Substituted Organosilicon Compounds 468
4.4.18.3.4 Variation 4: Oxidation of Allyl-Substituted Organosilicon Compounds 469
4.4.18.3.5 Variation 5: Oxidation of Alkyl-Substituted Organosilicon Compounds 469
4.4.19 Product Subclass 19: Silyl Sulfides and Selenides 474
Synthesis of Product Subclass 19 476
4.4.19.1 Method 1: From Hydrogen Sulfide and Aminosilanes 476
4.4.19.2 Method 2: From Thiolates and Halosilanes 477
4.4.19.2.1 Variation 1: From Enethiolates and Halosilanes 478
4.4.19.3 Method 3: From In Situ Generated Selenolates and Halosilanes 479
4.4.19.3.1 Variation 1: From Lithium, Powdered Selenium, and Chlorotrimethylsilane 479
4.4.20 Product Subclass 20: Silyl Azides 482
Synthesis of Product Subclass 20 482
4.4.20.1 Method 1: Synthesis of Silyl Azides by Substitution 482
4.4.20.1.1 Variation 1: From Silyl Halides 482
4.4.20.1.2 Variation 2: From N-Butyltrialkylsilanamines 483
4.4.20.2 Method 2: Synthesis of Silyl Azides by Trans-silylations 483
Applications of Product Subclass 20 in Organic Synthesis 484
4.4.20.3 Method 3: Synthesis of Heterocyclic Compounds Using Silyl Azides 484
4.4.20.3.1 Variation 1: Triazoles 484
4.4.20.3.2 Variation 2: Tetrazoles 485
4.4.20.3.3 Variation 3: Other Heterocycles 485
4.4.20.4 Method 4: Synthesis of Acyl Azides Using Silyl Azides 486
4.4.20.4.1 Variation 1: From Carboxylic Acid Derivatives 486
4.4.20.4.2 Variation 2: From Aldehydes 486
4.4.20.5 Method 5: Synthesis of a-Azido Alcohols Using Silyl Azides 487
4.4.20.6 Method 6: Synthesis of ß-Azido Alcohols Using Silyl Azides 487
4.4.20.6.1 Variation 1: From Epoxides 487
4.4.20.6.2 Variation 2: From 1,2-Diols 490
4.4.20.7 Method 7: Synthesis of ß-Azido Amines Using Silyl Azides 490
4.4.20.8 Method 8: Synthesis of Alkyl Azides Using Silyl Azides 491
4.4.20.8.1 Variation 1: Alkyl Azides 491
4.4.20.8.2 Variation 2: ß-Azido Ketones 492
4.4.20.8.3 Variation 3: Aryl Azides 492
4.4.20.8.4 Variation 4: Miscellaneous 492
4.4.20.9 Method 9: Applications of Silyl Azides in Rearrangement and in Oxidation Reactions 493
4.4.21 Product Subclass 21: Silylamines 498
Synthesis of Product Subclass 21 498
4.4.21.1 Method 1: Reaction of Chlorosilanes with Amines 498
4.4.21.1.1 Variation 1: Preparation of Diethylamino- and Diisopropylamino-Substituted Silane Derivatives 499
4.4.21.1.2 Variation 2: Preparation and ortho-Lithiation of N,N'-Bis[2-(dimethylamino)ethyl]-N,N'-dimethyldiphenylsilanediamine 500
4.4.21.1.3 Variation 3: Reaction of Chloro{2-[chloro(dimethyl)silyl]ethyl}-dimethylsilane with Primary Amines 501
4.4.21.1.4 Variation 4: Reaction of Bis(dimethylsilyl)benzene with Primary Amines 502
4.4.21.2 Method 2: Reaction of Silyl Trichloroacetates with Amines 502
4.4.21.3 Method 3: Reaction of Tris(2-aminoethyl)amines with Tris- and Tetrakis(dimethylamino)silanes 503
4.4.21.4 Method 4: Reaction of Silyllithiums with Amines 504
4.4.21.5 Method 5: Reaction of Hexamethyldisilazane 504
4.4.21.5.1 Variation 1: Preparation and Reaction of N,O-Bis(trimethylsilyl)hydroxylamine 504
4.4.21.5.2 Variation 2: Preparation of N,O-Bis(trimethylsilyl) Sulfamate 505
4.4.21.5.3 Variation 3: Monosilylation of Anilines 506
4.4.21.5.4 Variation 4: Preparation and Reaction of Lithium N,N-Bis(trimethylsilyl)(aminomethyl)acetylide 506
4.4.21.5.5 Variation 5: Preparation of N-Silylaldimines 508
4.4.21.5.6 Variation 6: Preparation of N,N,N'-Tris(trimethylsilyl)amidines 508
4.4.21.6 Method 6: Preparation of 1-Aza-2-silacyclobutanes 509
4.4.21.6.1 Variation 1: Aza-Brook Rearrangement of (a-Silylallyl)amines to N-Silylenamines 509
4.4.21.7 Method 7: Preparation and Reaction of Aminosilyl Anions 510
4.4.21.8 Method 8: Reaction of 1-(Trimethylsilyl)-1H-1,2,3-benzotriazole 511
4.4.21.8.1 Variation 1: Reaction of 2-Aza-1,3-dienes with Trimethylsilyl Trifluoromethanesulfonate 512
4.4.21.8.2 Variation 2: Reductive Silylation of Azaaromatic Compounds 512
4.4.21.8.3 Variation 3: Synthesis of N,N'-Disilylated Enediamines 513
4.4.21.8.4 Variation 4: Preparation of Diazasilacycloalkenes 513
4.4.21.8.5 Variation 5: Reductive Silylation of Nitriles 514
4.4.21.9 Method 9: Hydrosilylation of Imines 514
4.4.21.9.1 Variation 1: Hydrosilylation of Carbodiimides 515
4.4.21.9.2 Variation 2: Hydrosilylation of Nitriles 515
4.4.21.10 Method 10: Preparation of Stable Silanimines 516
4.4.21.11 Method 11: Preparation of a Lithium Silaamidide 517
4.4.21.12 Method 12: Preparation and Reaction of Stable Cyclic Bis(amino)silylenes 517
4.4.22 Product Subclass 22: Silyl Phosphines 520
Synthesis of Product Subclass 22 521
4.4.22.1 Method 1: From Silyl Hydrides 521
4.4.22.2 Method 2: From Silyl Halides 522
4.4.22.3 Method 3: From Other Silyl Phosphines 524
4.4.22.4 Additional Methods 525
4.4.23 Product Subclass 23: Silylmethyl Anions 528
4.4.23.1 Method 1: Metalation of Alkylsilanes and Their Derivatives 532
4.4.23.1.1 Variation 1: With Alkyllithiums 533
4.4.23.1.2 Variation 2: With Schlosser's Base 534
4.4.23.1.3 Variation 3: With Lithium Diisopropylamide and Similar Amide Bases 534
4.4.23.1.4 Variation 4: With Other Bases 535
4.4.23.2 Method 2: Metal--Halogen Exchange of a-Haloalkylsilanes 535
4.4.23.2.1 Variation 1: With Magnesium 536
4.4.23.2.2 Variation 2: With Lithium 537
4.4.23.3 Method 3: Transmetalation Reactions of a-Silylalkylmetals 538
4.4.23.3.1 Variation 1: Of a-Silylalkyllithium Compounds 538
4.4.23.3.2 Variation 2: Of a-Silylalkylmagnesium 539
4.4.23.3.3 Variation 3: Of a-Silylalkylstannane 539
4.4.23.4 Method 4: Reductive Lithiation of a-Sulfanyl- and a-Selanylalkylsilanes 540
4.4.23.5 Method 5: Addition of Organometallic Reagents to Vinylsilanes and Their Analogues 541
4.4.23.5.1 Variation 1: Of Organolithium Reagents to Vinylsilanes 541
4.4.23.5.2 Variation 2: Of Organomagnesium Reagents to Vinylsilanes 542
4.4.23.6 Additional Methods 542
4.4.24 Product Subclass 24: Silyl Cyanides 546
4.4.24.1 Tetracoordinate Silyl Cyanides 546
4.4.24.1.1 Method 1: From Silyl Chlorides 547
4.4.24.1.1.1 Variation 1: Using Silver(I) or Mercury(II) Cyanide 548
4.4.24.1.1.2 Variation 2: Using Lithium Cyanide 548
4.4.24.1.1.3 Variation 3: Using Sodium or Potassium Cyanide 549
4.4.24.1.1.4 Variation 4: Using Tetraethylammonium Cyanide 549
4.4.24.1.1.5 Variation 5: Using Hydrogen Cyanide and Triethylamine 550
4.4.24.1.1.6 Variation 6: By Transcyanation 550
4.4.24.1.1.7 Variation 7: Using Acetonitrile 550
4.4.24.1.2 Method 2: From Other Silyl Halides 551
4.4.24.1.3 Method 3: By Cleavage of a Si--O Bond 552
4.4.24.1.4 Method 4: By Cleavage of a Si--S Bond 553
4.4.24.1.5 Method 5: By Cleavage of a Si--N Bond 554
4.4.24.1.6 Method 6: By Cleavage of a Si--C Bond 554
4.4.24.1.7 Method 7: By Cleavage of a Si--Si Bond 554
4.4.24.1.8 Method 8: By Cleavage of a Si--H Bond 555
4.4.24.1.9 Method 9: By Cleavage of a Si--Hg Bond 556
4.4.24.2 Pentacoordinate Silyl Cyanides 556
4.4.25 Product Subclass 25: Acylsilanes 560
Synthesis of Product Subclass 25 561
4.4.25.1 Simple Acylsilanes 561
4.4.25.1.1 Method 1: Hydroboration--Oxidation of Alkynylsilanes 562
4.4.25.1.2 Method 2: Hydrolysis of Acetals 562
4.4.25.1.3 Method 3: From Silylmetal Intermediates 565
4.4.25.1.4 Method 4: Preparation from Enol Ethers 568
4.4.25.1.5 Method 5: Palladium-Catalyzed Coupling 571
4.4.25.1.6 Method 6: Oxidation of a-Hydroxysilanes 571
4.4.25.1.7 Method 7: Silylation of Acylmetal Species 572
4.4.25.1.8 Method 8: Other Oxidative Methods 574
4.4.25.1.9 Additional Methods 575
4.4.25.2 a-Haloacylsilanes 576
4.4.25.2.1 Method 1: Halogenation of Trialk-1-enyl Borates 576
4.4.25.2.2 Method 2: Halogenation of the Enol Ethers of Acylsilanes 577
4.4.25.2.3 Method 3: Bromination--Rearrangement of Epoxysilanes 577
4.4.25.2.4 Additional Methods 578
4.4.25.3 a-Oxoacylsilanes 578
4.4.25.3.1 Method 1: Oxidation of Diols 578
4.4.25.3.2 Method 2: From Allenyl Ethers 579
4.4.25.3.3 Method 3: From Silyldiazoesters 579
4.4.25.4 a,ß-Unsaturated Acylsilanes 579
4.4.25.4.1 Method 1: From Allenyl Ethers 580
4.4.25.4.2 Method 2: Other Enol Ether Methods 582
4.4.25.4.3 Method 3: Hydroboration--Oxidation of Enynylsilanes and (Arylalkynyl)silanes 584
4.4.25.4.4 Method 4: From Alk-2-ynoylsilanes 585
4.4.25.4.5 Method 5: Oxidation of a-Hydroxysilanes 585
4.4.25.4.6 Additional Methods 586
4.4.25.5 a-Cyclopropylacylsilanes 587
4.4.25.5.1 Method 1: From Silylmetal Species 588
4.4.25.5.2 Method 2: From a-Haloacylsilanes 588
4.4.25.5.3 Additional Methods 589
4.4.25.6 a-Epoxyacylsilanes 590
4.4.25.6.1 Method 1: Epoxidation of a,ß-Unsaturated Acylsilanes 590
Applications of Product Subclass 25 in Organic Synthesis 590
4.4.25.7 Simple Acylsilanes 590
4.4.25.7.1 Method 1: Nucleophilic Addition 590
4.4.25.7.2 Method 2: Acylsilanes as Acyl Anion Precursors 597
4.4.25.7.3 Method 3: Enolate and Enol Ether Reactions 598
4.4.25.7.4 Method 4: Photochemistry 599
4.4.25.7.5 Method 5: Biotransformations 601
4.4.25.7.6 Method 6: Miscellaneous 602
4.4.25.8 a-Haloacylsilanes 602
4.4.25.9 a-Oxoacylsilanes 604
4.4.25.10 a,ß-Unsaturated Acylsilanes 605
4.4.26 Product Subclass 26: 1-Diazo-1-silylalkanes 616
Synthesis of Product Subclass 26 618
4.4.26.1 Method 1: From Trialkyl(chloromethyl)silanes by Diazo Transfer Reactions 618
4.4.26.2 Method 2: From Acylsilanes 620
4.4.26.3 Method 3: Silylation of a-Diazoacetates, a-Diazophosphonates, and a-Diazo Ketones 620
4.4.26.4 Method 4: Alkylation of Diazo(trimethylsilyl)methane 621
4.4.26.5 Method 5: Acylation of Diazo(pentamethyldisilanyl)methane 621
4.4.26.6 Method 6: Silylation of Diazo(trimethylsilyl)methane 622
4.4.27 Product Subclass 27: a-Haloalkylsilanes 626
Synthesis of Product Subclass 27 627
4.4.27.1 Method 1: Direct Halogenation of Alkylsilanes 627
4.4.27.1.1 Variation 1: Chlorination of Alkylsilanes 628
4.4.27.1.2 Variation 2: Bromination of Alkylsilanes 628
4.4.27.2 Method 2: Substitution of a-Hydroxyalkylsilanes 629
4.4.27.2.1 Variation 1: Substitution with Chloride Using Thionyl Chloride 630
4.4.27.2.2 Variation 2: Chlorination of a-Hydroxyalkylsilanes with Triphenylphosphine and Carbon Tetrachloride 631
4.4.27.2.3 Variation 3: Iodination of a-Hydroxyalkylsilanes with Methyl(triphenoxy)phosphonium Iodide 631
4.4.27.3 Method 3: Haloalkylation of Halosilanes 632
4.4.27.4 Method 4: Reaction of Halosilanes with Diazomethane 633
4.4.27.5 Method 5: Nucleophilic Substitution of Halo(haloalkyl)silanes 634
4.4.27.6 Method 6: Alkylation of a-Haloalkylsilanes 635
Applications of Product Subclass 27 in Organic Synthesis 635
4.4.28 Product Subclass 28: a-Silyl Alcohols, Ethers, and Amines 642
Synthesis of Product Subclass 28 644
4.4.28.1 Method 1: From Silyl Hydrides and Fischer Alkoxycarbene Complexes 644
4.4.28.2 Method 2: From Silyl Hydrides and N-Vinylamides or N-Vinylureas 644
4.4.28.3 Method 3: From Silyl Halides and Ethers or Amines 645
4.4.28.3.1 Variation 1: Deprotonative a-Silylation of Aliphatic Ethers with Lithium-free Butylpotassium and Chlorosilanes 645
4.4.28.3.2 Variation 2: Deprotonative a-Silylation of Alkyl Arylmethyl Ethers with tert-Butyllithium/N,N,N',N'-Tetramethylethylenediamine and Chlorosilanes 646
4.4.28.3.3 Variation 3: Deprotonative a-Silylation of Cyclic Secondary N-tert-Butoxycarbonyl Amines with sec-Butyllithium/N,N,N',N'-Tetramethylethylenediamine or sec-Butyllithium/(-)-Sparteine and Chlorosilanes 647
4.4.28.3.4 Variation 4: Dehalogenative Silylation of Chloromethyl Ethers with Lithium and Chlorosilanes 648
4.4.28.3.5 Variation 5: Desulfurative Silylation of a-Phenylsulfanyl Ethers with Lithium 1-(Dimethylamino)naphthalenide and Chlorosilanes 648
4.4.28.4 Method 4: From Silyl Halides and Aldehydes or Ketones by Reductive Silylation with Magnesium 649
4.4.28.5 Method 5: From Silyl Halides and Esters by Reductive Silylation with Magnesium or Sodium 650
4.4.28.5.1 Variation 1: Reductive Silylation of tert-Butyl or Trimethylsilyl Benzoates with the Chlorotrimethylsilane/Magnesium/Hexamethyl-phosphoric Triamide System 651
4.4.28.5.2 Variation 2: Reductive Silylation of Trimethylsilyl Alkanoates with the Chlorotrimethylsilane/Sodium/Tetrahydrofuran System 651
4.4.28.6 Method 6: From Silyl Halides and Cyanides or O-Trimethylsilyl Cyanohydrins by Reductive Silylation with Lithium 652
4.4.28.7 Method 7: From O-Silyl Ethers 653
4.4.28.7.1 Variation 1: Retro-[1,2]-Brook Rearrangement of Allyl and Benzyl O-Silyl Ethers 653
4.4.28.7.2 Variation 2: Retro-[1,2]-Brook Rearrangement of a-Stannyl Silyl Ethers 654
4.4.28.8 Method 8: From Silyl Anions and Aldehydes or Ketones 655
4.4.28.8.1 Variation 1: With Trimethylsilyllithium 656
4.4.28.8.2 Variation 2: With Tris(trimethylsilyl)aluminum--Diethyl Ether Complex 657
4.4.28.8.3 Variation 3: With Disilanes by Fluoride-Induced Catalysis 657
4.4.28.8.4 Variation 4: With Dimethylphenylsilyllithium 658
4.4.28.9 Method 9: From Silyl Anions and Esters 659
4.4.28.10 Method 10: From (a-Haloalkyl)silanes and Nitrogen or Oxygen Nucleophiles 660
4.4.28.10.1 Variation 1: N-Alkylation of Primary or Secondary Amines 660
4.4.28.10.2 Variation 2: O- and N-Alkylation of Masked Hydroxy or Amino Groups 661
4.4.28.11 Method 11: From a-Metallosilanes 662
4.4.28.12 Method 12: From Acylsilanes 663
4.4.28.12.1 Variation 1: Via Asymmetric Reduction with B-Chlorodiisopinocampheylborane 663
4.4.28.12.2 Variation 2: Via Samarium(II) Iodide Promoted Reductions and Alkylations 664
4.4.28.12.3 Variation 3: Via Addition of Organolithium or Organomagnesium Reagents 665
4.4.28.12.4 Variation 4: Via Barbier-type Addition of Organoindium Reagents 666
4.4.28.13 Method 13: From Vinylsilanes 667
4.4.28.13.1 Variation 1: Via Hydroboration 667
4.4.28.13.2 Variation 2: Via Catalytic Dihydroxylation with Osmium Tetroxide 668
4.4.28.14 Method 14: Modification of Existing a-Silyl Alcohols or Ethers 669
4.4.28.14.1 Variation 1: Via syn-Dihydroxylation of a-Silyl-a-vinyl Alcohols (a-Hydroxyallylsilanes) with Osmium Tetroxide 669
4.4.28.14.2 Variation 2: Via O-Alkylation of a-Silyl Alcohols with Allyl and Benzyl Trichloroacetimidoates Catalyzed by Lewis Acids 670
4.4.28.14.3 Variation 3: Via Addition of a-Lithio-a-silyl Ethers to Aldehydes or Ketones 670
4.4.28.15 Method 15: Modification of Existing a-Silyl Amines: a-Alkylation or a-Arylation of a-Silylamines with Grignard Reagents 671
4.4.28.16 Additional Methods 672
Applications of Product Subclass 28 in Organic Synthesis 673
4.4.29 Product Subclass 29: a,ß-Epoxysilanes 680
Synthesis of Product Subclass 29 680
4.4.29.1 Method 1: By Reaction of Lithiated a-Halosilanes with Aldehydes or Ketones 680
4.4.29.2 Method 2: By Epoxidation of a Vinylsilane 682
4.4.29.2.1 Variation 1: Reaction with a Peroxy Acid 682
4.4.29.2.2 Variation 2: Sharpless Epoxidation of a Silylated Allylic Alcohol 683
4.4.29.3 Method 3: By Reaction of an a-Metalated Epoxide 683
Applications of Product Subclass 29 in Organic Synthesis 684
4.4.29.4 Method 4: Reduction by Complex Hydrides 684
4.4.29.5 Method 5: Reaction with Organometallic Reagents 685
4.4.29.6 Method 6: Reaction with Heteroatom Nucleophiles 686
4.4.29.7 Method 7: Ring Opening/Desilylation to Aldehydes or Ketones 687
4.4.29.8 Method 8: Protodesilylation to Epoxides 688
4.4.29.9 Method 9: Formation of a-Alkoxy Ketones via Allene Epoxides 688
4.4.29.10 Method 10: Rearrangement to a-Silylaldehydes or a-Silyl Ketones 689
4.4.29.11 Method 11: Rearrangement to Silyl Enol Ethers 690
4.4.29.12 Method 12: Rearrangement to C-Silylated Allylic Alcohols 690
4.4.29.13 Method 13: Rearrangement to Allylic Silanols 691
4.4.29.14 Method 14: a-Metalation 692
4.4.30 Product Subclass 30: Alkynyl[Ethynyl]silanes 694
Synthesis of Product Subclass 30 694
4.4.30.1 Method 1: Reaction of Alkynes with Hydrosilanes via Dehydrogenative Coupling 694
4.4.30.2 Method 2: Reactions of Alkynylmetals with Silyl Halides 694
4.4.30.2.1 Variation 1: Of Chlorosilanes with Ethynylmagnesium Reagents 695
4.4.30.2.2 Variation 2: Of Chlorosilanes with Ethynyllithium Reagents 695
4.4.30.2.3 Variation 3: Of Chlorosilanes with Ethynylzinc Reagents 696
4.4.30.3 Method 3: Reactions of Ethynyl(trimethyl)silane or Bis(trimethysilyl)ethyne 696
4.4.30.3.1 Variation 1: The Sonogashira--Hagihara Reaction of Ethynyl(trimethyl)silane 696
4.4.30.3.2 Variation 2: Reactions of Bis(trimethylsilyl)ethyne with Various Organic Electrophiles 697
4.4.30.4 Methods 4: Additional Methods 697
Applications of Product Subclass 30 in Organic Synthesis 698
4.4.30.5 Method 5: Reactions of Ethynylsilanes with Carbonyl Compounds 698
4.4.30.6 Method 6: Asymmetric Alkynylation of Chiral Acetals 699
4.4.30.7 Method 7: Alkynylation of Acid Chlorides in the Presence of a Copper(I) Salt 700
4.4.30.8 Method 8: Coupling Reactions of Ethynylsilanes in the Presence of Transition Metals 700
4.4.31 Product Subclass 31: Silylketenes 704
Synthesis of Product Subclass 31 705
4.4.31.1 Method 1: Elimination Reactions 705
4.4.31.2 Method 2: Thermolysis of (Alkoxyethynyl)silanes (1,5-Hydrogen Transfer) 706
4.4.31.3 Method 3: Rearrangement by 1,3-Silyl Shift 707
4.4.31.3.1 Variation 1: From Alkoxyalkynes 707
4.4.31.3.2 Variation 2: From 2-Phenyl-2,3-dihydrofuran or 3-Phenylisoxazole 708
4.4.31.4 Method 4: From Diazo Compounds via Wolff Rearrangement 709
4.4.31.4.1 Variation 1: Photolysis 709
4.4.31.4.2 Variation 2: Metal (Copper or Rhodium) Catalysis 709
4.4.31.5 Method 5: Thermolysis or Photolysis of Cyclobutenediones or Cyclobutenones 710
Applications of Product Subclass 31 in Organic Synthesis 710
4.4.31.6 Method 6: Formation of ß-Lactones via Lewis Acid Promoted [2 + 2]-Cycloaddition Reaction 711
4.4.31.7 Method 7: Formation of Aza-Allenic Derivatives and Their Further Electrocyclization 711
4.4.32 Product Subclass 32: Allenylsilanes 716
Synthesis of Product Subclass 32 717
4.4.32.1 Method 1: From Lithiated Allenes and Trialkylhalosilanes 717
4.4.32.2 Method 2: From Allenyl Ethers 718
4.4.32.3 Method 3: From C-Silylated Propargylic Alcohols 718
4.4.32.3.1 Variation 1: Via Organocuprates 719
4.4.32.3.2 Variation 2: Via Grignard Reagents 719
4.4.32.3.3 Variation 3: Via Arylsulfonohydrazides 720
4.4.32.4 Method 4: From C-Silylated Propargylic Esters and Organoheterocuprates 720
4.4.32.4.1 Variation 1: From Silyl-Substituted Propargylic Sulfinates 720
4.4.32.4.2 Variation 2: From Silyl-Substituted Propargylic Sulfonates 721
4.4.32.5 Method 5: Silylcupration of Propargylic Esters 722
4.4.32.5.1 Variation 1: Silylcupration of Propargylic Acetates 722
4.4.32.5.2 Variation 2: Silylcupration of Propargylic Carbamates 723
4.4.32.6 Method 6: From Propargylsilanes 724
4.4.32.7 Method 7: From Silyl-Substituted Ynones 725
4.4.32.8 Method 8: From Silyl-Substituted Propargylboranes 725
4.4.32.9 Method 9: From Chloroenynes 726
4.4.32.10 Method 10: From Bromoallenes 726
4.4.32.11 Method 11: Via Amide Acetal Claisen Rearrangement of Propargylic Alcohols 727
4.4.32.12 Method 12: Chain Elongation of Allenylsilanes 727
4.4.32.13 Additional Methods 728
4.4.33 Product Subclass 33: Arylsilanes 732
Synthesis of Product Subclass 33 732
4.4.33.1 Method 1: Via the Würtz--Fittig Reaction 732
4.4.33.2 Method 2: Silylation of Aryl-Substituted Metals 733
4.4.33.2.1 Variation 1: Via Grignard Reagents 734
4.4.33.2.2 Variation 2: Via Organolithium Reagents 735
4.4.33.2.3 Variation 3: Via Reductive Silylation Followed by Oxidation 736
4.4.33.2.4 Variation 4: Via Halogen--Metal Exchange 736
4.4.33.3 Method 3: Electrophilic Aromatic Substitutions 737
4.4.33.4 Method 4: From Transition-Metal-Catalyzed Reactions 738
4.4.33.4.1 Variation 1: From Palladium Reagents 738
4.4.33.4.2 Variation 2: From Nickel and Rhodium Reagents 740
4.4.33.5 Method 5: From Cycloaddition Reactions 741
4.4.33.5.1 Variation 1: Via [2 + 3]-Dipolar Cycloadditions 741
4.4.33.5.2 Variation 2: Via [4 + 2] Cycloadditions 742
4.4.33.5.3 Variation 3: Via [2 + 2 + 2] Cycloadditions 743
4.4.33.6 Method 6: Via Silyl Migrations 744
4.4.33.6.1 Variation 1: Via [1,3] Oxygen-to-Carbon Silyl Migrations 744
4.4.33.6.2 Variation 2: Via [1,4] Oxygen-to-Carbon Silyl Migrations 745
4.4.33.7 Method 7: Via Photochemical Reactions 746
4.4.33.8 Method 8: Via Electrochemical Reactions 747
4.4.33.9 Methods 9: Additional Methods 748
Applications of Product Subclass 33 in Organic Synthesis 748
4.4.33.10 Method 10: Ipso-Substitution Reactions 748
4.4.33.11 Method 11: Oxidation of the C--Si Bond 749
4.4.33.12 Method 12: Cross-Coupling Reactions 750
4.4.33.13 Method 13: Protection of Hydroxy Groups 752
4.4.33.14 Method 14: Use as a Blocking Group 753
4.4.33.15 Method 15: Use as Traceless Linkers in Solid-Phase Synthesis 754
4.4.33.16 Method 16: Use as Fluorous Labels for Fluorous Synthesis 755
4.4.34 Product Subclass 34: Vinylsilanes 760
Synthesis of Product Subclass 34 760
4.4.34.1 Method 1: Vinylsilanes from Vinylmetal Compounds and Halosilanes 760
4.4.34.1.1 Variation 1: From Vinylcopper and Trialkylhalosilanes 760
4.4.34.1.2 Variation 2: From Vinylmagnesium Halides and Trialkyl- and Triarylhalosilanes 761
4.4.34.1.3 Variation 3: From Vinylsodium and Trialkylhalosilanes 762
4.4.34.1.4 Variation 4: From Vinyllithium and Trialkylhalosilanes 762
4.4.34.1.5 Variation 5: Using Metalated Vinylsilanes 764
4.4.34.2 Method 2: Coupling Reaction of Vinyl Halides with Silylmetal Species 766
4.4.34.3 Method 3: Addition--Elimination of Disilane to Vinyl Halides 767
4.4.34.4 Method 4: Coupling Reaction of (a- or ß-Halovinyl)silanes with Silylmetal Species 768
4.4.34.5 Method 5: Stille Coupling of Vinyl Halides with Trimethyl[(E)-2-(trimethylstannyl)vinyl]silane 770
4.4.34.6 Method 6: Reaction of Carbonyl Compounds with (Trimethylsilyl)methylmetal Species 771
4.4.34.6.1 Variation 1: Reaction of Aldehydes with Bis(trimethylsilyl)methyllithium 771
4.4.34.6.2 Variation 2: Reaction of Aldehydes with Bromobis(trimethylsilyl)methyllithium: Preparation of (a-Bromovinyl)silanes 772
4.4.34.6.3 Variation 3: Reaction of Carbonyl Compounds with Dimetal Species Derived from (Dibromomethyl)(trimethyl)silane 774
4.4.34.7 Method 7: By Wittig Reaction 775
4.4.34.8 Method 8: From Allylsilane Lithium Salt 776
4.4.34.9 Method 9: Dehydrogenative Silylation of Alkenes 776
4.4.34.10 Method 10: Heck-type Reaction 777
4.4.34.11 Method 11: Hydrogenation of Alkynylsilanes 778
4.4.34.12 Method 12: Hydrometalation of Alkynylsilanes 779
4.4.34.12.1 Variation 1: Hydrostannylation of Alkynylsilanes 779
4.4.34.12.2 Variation 2: Hydroalumination of Alkynylsilanes 779
4.4.34.12.3 Variation 3: Hydromagnesiation of Alkynylsilanes 781
4.4.34.13 Method 13: Carbocupration of Alkynylsilanes 782
4.4.34.14 Method 14: From Low-Valent Titanium Alkoxide--Alkynylsilane Complexes 782
4.4.34.15 Method 15: Radical Addition of Iodoalkanes to Alkynylsilanes 783
4.4.34.16 Method 16: [2 + 4] or [2 + 2] Cycloadditions of Alkynylsilanes 784
4.4.34.17 Method 17: Cyclization of Alk-.-en-a-ylsilanes 784
4.4.34.18 Method 18: Silylmetalation of Terminal Alkynes 785
4.4.34.19 Method 19: Hydrosilylation 787
4.4.34.19.1 Variation 1: Hydrosilylation of Alkynes 787
4.4.34.19.2 Variation 2: Transition-Metal-Catalyzed Hydrosilylative Cyclization of Dialkynes 789
4.4.34.20 Method 20: Birch Reduction of Arylsilanes 790
Applications of Product Subclass 34 in Organic Synthesis 790
4.4.34.21 Method 21: Proto- and Deuterodesilylation 791
4.4.34.22 Method 22: Cleavage of the Vinyl C--Si Bond with Tetrabutylammonium Fluoride 791
4.4.34.23 Method 23: Electrophilic Substitution with Halogens 792
4.4.34.24 Method 24: Friedel--Crafts Acylation 793
4.4.34.25 Method 25: Formylation of Vinylsilanes 794
4.4.34.26 Method 26: Nazarov Cyclization 794
4.4.34.27 Method 27: Diels--Alder Reaction of (1E-Buta-1,3-dienyl)trimethylsilanes 795
4.4.34.28 Method 28: Annulation Reaction of 3-(Trimethylsilyl)but-3-en-2-one 796
4.4.34.29 Method 29: Preparation of Allenes 798
4.4.34.30 Method 30: Preparation of Carboxylic Acids from Terminal Alkynes 799
4.4.34.31 Method 31: Use as a Masked Carbonyl Group 799
4.4.34.32 Method 32: Vinyl Heck Reaction 800
4.4.34.33 Method 33: Palladium-Catalyzed Coupling 800
4.4.34.34 Method 34: Generation of Vinylidene Carbene 801
4.4.35 Product Subclass 35: a-Silyl Carbonyl Compounds 804
Synthesis of Product Subclass 35 808
4.4.35.1 Method 1: C-Silylation of Enolates and Derivatives 808
4.4.35.1.1 Variation 1: Of Chiral Hydrazones 809
4.4.35.2 Method 2: Oxidation of ß-Hydroxysilanes 810
4.4.35.3 Method 3: Metal--Carbenoid Insertion into the Si--H Bond 810
4.4.35.4 Method 4: Addition of Nucleophiles to a-Silyl Ketenes 811
4.4.35.5 Method 5: Addition of a-Silyl Organometallic Reagents to Carbonyl Precursors 813
4.4.35.6 Method 6: Rearrangements 813
4.4.35.6.1 Variation 1: Isomerization of a,ß-Epoxysilanes 814
4.4.35.6.2 Variation 2: [1,3]-Oxygen-to-Carbon Migration of a Silicon Group 815
4.4.35.7 Additional Methods 816
4.4.36 Product Subclass 36: ß-Silyl Alkyl Halides 820
Synthesis of Product Subclass 36 821
4.4.36.1 Method 1: Addition of Hydrogen Halides to Allylsilane and Vinylsilanes 821
4.4.36.2 Method 2: Addition of Halogens to Allylsilane and Vinylsilanes 822
4.4.36.3 Method 3: Addition of Sulfur and Selenium Halides to Vinylsilanes and Allylsilanes 823
4.4.36.4 Method 4: Addition of Radicals 824
4.4.36.5 Method 5: Formation of (2-Halocyclopropyl)silanes by Addition of Halocarbenes to Alkenylsilanes and Allenylsilanes 825
4.4.36.6 Method 6: From Allylic Substitution of 1,2-Dihaloallyl Groups Using Trimethylsilyllithium and Copper(I) Iodide Reagent 827
4.4.36.7 Method 7: From Halogenation of (2-Hydroxyalkyl)silanes 827
4.4.36.8 Method 8: From Halogenation of ß-Silyl Carbonyl Compounds, a-Silylenol Ethers, or a-Silylenolates 828
4.4.36.8.1 Variation 1: From ß-Silyl Carbonyl Compounds 829
4.4.36.8.2 Variation 2: From a-Silylenol Ethers or a-Silylenolates of Acylsilanes 829
4.4.36.9 Additional Methods 830
Applications of Product Subclass 36 in Organic Synthesis 831
4.4.37 Product Subclass 37: ß-Silyl Alcohols and the Peterson Reaction 836
Synthesis of Product Subclass 37 838
4.4.37.1 Method 1: Direct Deprotonation of a Silane and Addition to a Carbonyl Compound 838
4.4.37.2 Method 2: From Silylmethylmagnesium Halides and Carbonyl Compounds 839
4.4.37.2.1 Variation 1: Grignard and Organolithium Reagents 839
4.4.37.2.2 Variation 2: Use of Organocerium Reagents 840
4.4.37.2.3 Variation 3: Formation of Vinyllithium Reagents 841
4.4.37.3 Method 3: Generation of the a-Silyl Carbanion by Transmetalation 841
4.4.37.3.1 Variation 1: Displacement of a Phenylsulfanyl Group by Lithium Naphthalenide 842
4.4.37.3.2 Variation 2: Displacement of a Phenylsulfanyl Group by Lithium 1-(Dimethylamino)naphthalenide 842
4.4.37.3.3 Variation 3: Displacement of a Tin Group 843
4.4.37.4 Method 4: Preparation of Vinyl Ethers and Other Heteroatom-Substituted Alkenes 843
4.4.37.4.1 Variation 1: Preparation of Enol Ethers 844
4.4.37.4.2 Variation 2: Preparation of Vinyl Sulfides 844
4.4.37.4.3 Variation 3: Preparation of Vinyl Sulfones 845
4.4.37.4.4 Variation 4: Preparation of Vinylphosphonates 845
4.4.37.4.5 Variation 5: Preparation of Vinylstannanes 845
4.4.37.4.6 Variation 6: Preparation of Difunctional Alkenes 846
4.4.37.5 Method 5: Preparation of a,ß-Unsaturated Carbonyl Compounds 846
4.4.37.5.1 Variation 1: Formation of a,ß-Unsaturated Esters 847
4.4.37.5.2 Variation 2: Formation of a,ß-Unsaturated Esters with Lithium Dicyclohexylamide as Base 847
4.4.37.6 Method 6: Preparation of a,ß-Unsaturated Nitriles 847
4.4.37.7 Method 7: Preparation of Enals Through Imines 848
4.4.37.8 Method 8: Reduction of a-Silyl Carbonyl Compounds 848
4.4.37.9 Method 9: Additions of Organometallic Reagents to a-Silyl Carbonyl Compounds 849
4.4.37.9.1 Variation 1: Addition of an Organometallic Reagent to an a-Silyl Ketone 849
4.4.37.9.2 Variation 2: Addition of an Organometallic Reagent to an a-Silyl Ester 850
4.4.37.10 Method 10: Addition of a Silylmetal to an Epoxide 851
4.4.37.11 Method 11: Vinylsilanes and Alkyllithiums with Carbonyl Compounds 851
4.4.38 Product Subclass 38: Propargylsilanes 858
Synthesis of Product Subclass 38 859
4.4.38.1 Method 1: From Propargylmagnesium Halides and Trialkyl- and Triarylsilicon Halides 859
4.4.38.1.1 Variation 1: Generation of the Grignard Reagent In Situ (Barbier Procedure) 859
4.4.38.1.2 Variation 2: Silylation of a Preformed Grignard Reagent 860
4.4.38.2 Method 2: From Alk-1-ynes 860
4.4.38.2.1 Variation 1: Coupling with (Halomethyl)trimethylsilane 860
4.4.38.2.2 Variation 2: Coupling with Trimethylsilylmethyl Trifluoromethanesulfonate 861
4.4.38.3 Method 3: From Alk-2-ynes 862
4.4.38.4 Method 4: From 1,3-Dilithiated Alk-1-ynes 862
4.4.38.5 Method 5: From 1-(Trimethylsilyl)alk-1-ynes 863
4.4.38.6 Method 6: From 1,3-Bis(trimethylsilyl)alk-1-ynes 864
4.4.38.7 Method 7: From 1-Bromoalk-1-ynes 864
4.4.38.7.1 Variation 1: Via Asymmetric Grignard Cross Coupling 864
4.4.38.7.2 Variation 2: Via Borinate Ester Cross Coupling 865
4.4.38.8 Method 8: From Benzyl Propargyl Ethers 865
4.4.38.9 Method 9: From a-Silylated Aldehydes 866
4.4.38.10 Method 10: From ß-Silylated Esters 867
4.4.38.11 Method 11: Chain Elongation from the Propargylic Carbon of Trimethyl(propargyl)silanes 867
4.4.38.12 Method 12: Chain Elongation from the Acetylenic Carbon of Trimethyl(propargyl)silanes 868
4.4.38.13 Additional Methods 869
4.4.39 Product Subclass 39: Benzylsilanes 872
Synthesis of Product Subclass 39 872
4.4.39.1 Method 1: From Benzylic Hydrogens 872
4.4.39.2 Method 2: From Benzylic Halogens 874
4.4.39.2.1 Variation 1: Via Benzylmagnesium Reagents 874
4.4.39.2.2 Variation 2: Via Benzyllithium Reagents 875
4.4.39.3 Method 3: By Substitution of Aromatic Hydrogens 875
4.4.39.4 Method 4: By Substitution of Aromatic Halogens 876
4.4.39.5 Method 5: By Hydrosilylation of Styrene Derivatives 877
4.4.39.6 Method 6: By Addition of Silylmetal Reagents 878
4.4.39.7 Methods 7: Additional Methods 879
Applications of Product Subclass 39 in Organic Synthesis 879
4.4.39.8 Method 8: Benzylsilanes in Organic Synthesis 879
4.4.40 Product Subclass 40: Allylsilanes 884
Synthesis of Product Subclass 40 886
4.4.40.1 Method 1: From Allylmagnesium Halides and Trialkylhalosilanes 886
4.4.40.1.1 Variation 1: Silylation of a Preformed Grignard Reagent 887
4.4.40.1.2 Variation 2: Silylation of an In Situ Generated Grignard Reagent 888
4.4.40.2 Method 2: From Allylmagnesium Halides by Transition-Metal-Catalyzed Coupling with Hydrosilanes 888
4.4.40.3 Method 3: From Allyl Chlorides by Zinc-Mediated Silylation 889
4.4.40.4 Method 4: From Allyl Halides by Electroreductive Synthesis 889
4.4.40.5 Method 5: By Silylation of Metalated Alkenes 890
4.4.40.5.1 Variation 1: From Lithiated Alkenes 890
4.4.40.5.2 Variation 2: From Alkenylpotassium Compounds 891
4.4.40.6 Method 6: From Metalated Allyl Halides and Chlorotrimethylsilane 893
4.4.40.7 Method 7: From a-Heteroalkenes by Transition-Metal-Catalyzed Cross Coupling 893
4.4.40.7.1 Variation 1: From Vinyl Halides With [(Trimethylsilyl)methyl]magnesium Halides and Related Species 893
4.4.40.7.2 Variation 2: From Enol Phosphates with [(Trialkylsilyl)methyl]magnesium Halides 895
4.4.40.7.3 Variation 3: From Vinyl Trifluoromethanesulfonates with Tris[(trimethylsilyl)methyl]aluminum 895
4.4.40.8 Method 8: From a-Silyl Aldehydes and Alkylidinetriphenylphosphoranes by a Wittig Reaction 896
4.4.40.9 Method 9: From Carbonyl Compounds and Trialkyl[2-(trimethylsilyl)ethylidene]phosphoranes by a Wittig Reaction 897
4.4.40.9.1 Variation 1: Via a Preformed ß-Silylated Phosphonium Salt 897
4.4.40.9.2 Variation 2: Via an In Situ Generated ß-Silylated Phosphonium Salt 898
4.4.40.10 Method 10: From Carbonyl Compounds and Ethyl 2-(Diethoxyphosphoryl)-3-(trimethylsilyl)propanoate by Horner--Wadsworth--Emmons Reaction 898
4.4.40.11 Method 11: From Carbonyl Compounds and ß-Silyl Thioacetals by Titanium(II)-Promoted Reductive Alkenation 899
4.4.40.12 Method 12: From Carbonyl Compounds and Trimethyl[2-(phenylsulfonyl)ethyl]silane by the Julia Reaction 900
4.4.40.13 Method 13: Formation of Exocyclic Allylsilanes by the Ramberg--Bäcklund Reaction 901
4.4.40.14 Method 14: From 1,3-Dienes by Hydrosilylation 902
4.4.40.15 Method 15: From 1,3-Dienes by Carbosilylation 903
4.4.40.16 Method 16: From Allyl Halides by Copper(I)-Catalyzed Silylation with Trichlorosilane 904
4.4.40.17 Method 17: From Allenes by Palladium(0)-Catalyzed Carbosilylation 904
4.4.40.18 Method 18: From Lithium Allyl Alcoholates and Hexamethyldisilane 905
4.4.40.19 Method 19: From Allyl Esters via Allylpalladium(0) Complexes 906
4.4.40.19.1 Variation 1: Using Disilanes 906
4.4.40.19.2 Variation 2: Using Samarium(II) Iodide and Chlorotrimethylsilane 907
4.4.40.20 Method 20: From Allyl Alcohols by Palladium(0)-Catalyzed Intramolecular Silylsilylation 908
4.4.40.21 Method 21: Formation of Bis(allylsilanes) from 1,3-Dienes 909
4.4.40.22 Method 22: From Allyl Esters or Allyl Carbamates and a Silylcuprate Reagent 910
4.4.40.22.1 Variation 1: From Allyl Esters 910
4.4.40.22.2 Variation 2: From Allyl Carbamates 911
4.4.40.23 Method 23: From Allyl Halides and a Silylcopper Reagent 912
4.4.40.24 Method 24: Formation of 2-Substituted Allylsilanes by Silylcupration of Allene 913
4.4.40.25 Method 25: From Allyl Halides or Allyl Phosphates and a Silyllithium Reagent 914
4.4.40.25.1 Variation 1: From Allyl Halides 914
4.4.40.25.2 Variation 2: From Allyl Phosphates 915
4.4.40.26 Method 26: Formation of 1,3-Disubstituted Allylsilanes by Decarboxylative Elimination 916
4.4.40.27 Method 27: Formation of 1-Substituted Allylsilanes by Grieco Dehydration 918
4.4.40.28 Method 28: From Alkynes and a-Silyl Organocopper Reagents 919
4.4.40.28.1 Variation 1: Stoichiometric Carbocupration with a Copper(I) Salt 919
4.4.40.28.2 Variation 2: Copper-Catalyzed Carbometalation of Alk-2-yn-1-ols 920
4.4.40.29 Method 29: From Mixed Vinylcuprates and (Iodomethyl)trimethylsilane or Related Reagents 921
4.4.40.30 Method 30: From Carboxylic Acid Derivatives and an Organocerium Reagent by a Peterson-type Reaction 921
4.4.40.31 Method 31: From .-Silylated Allylic Alcohols by a Claisen Rearrangement 923
4.4.40.31.1 Variation 1: By a Johnson Ortho Ester Claisen Rearrangement 923
4.4.40.31.2 Variation 2: By an Ireland--Claisen Rearrangement 924
4.4.40.31.3 Variation 3: By the Eschenmoser Variant of the Claisen Rearrangement 925
4.4.40.32 Method 32: From 1-Trimethylsilyl-1,3-dienes by a Diels--Alder Reaction 926
4.4.40.33 Method 33: Formation of Cyclopentanoid Allylsilanes by an Intramolecular Ene Reaction 926
4.4.40.34 Method 34: From Alkenyl Fischer Carbene Complexes by a [2 + 1]-Insertion Reaction with Triorganosilanes 927
4.4.40.35 Method 35: From Vinyldiazo Carbonyl Compounds by a Rhodium-Catalyzed [2 + 1]-Insertion Reaction with Triorganosilanes 928
4.4.40.36 Method 36: Formation of Formyl-Substituted Alk-2-enylsilanes by Photolysis 929
4.4.40.37 Method 37: From Allyl Sulfides by Reductive Silylation 930
4.4.40.37.1 Variation 1: By Retro-[1,4]-Brook Rearrangement 930
4.4.40.37.2 Variation 2: By Silylation of Oxyanion--Carbanionic Species 930
4.4.40.38 Method 38: From Allyl Sulfides and Tris(trimethylsilyl)silane by a Radical Reaction 931
4.4.40.39 Method 39: From Allyl Sulfones 932
4.4.40.40 Method 40: Formation of 3-Substituted Allylsilanes by a Peterson-type Elimination 933
4.4.40.41 Method 41: Formation of 3-Substituted Allylsilanes by Silicon-Directed Bamford--Stevens Reaction 933
4.4.40.42 Method 42: From .-Silylated Allylic Esters or Allyl Carbonates by a Palladium(0)-Catalyzed Reduction 934
4.4.40.42.1 Variation 1: From Allylic Esters 934
4.4.40.42.2 Variation 2: From Allylic Carbonates 935
4.4.40.43 Method 43: From Alk-2-ynylsilanes by Hydroalumination 936
4.4.40.44 Method 44: From Prop-2-ynylsilanes by Hydroboration 937
4.4.40.45 Method 45: From Alk-2-ynylsilanes by Catalytic Hydrogenation 937
4.4.40.46 Method 46: Formation of Exocyclic Allylsilanes by Intramolecular Reductive Heck Cyclization of Alk-2-ynylsilanes 938
4.4.40.47 Method 47: Formation of 3-Substituted Allylsilanes by Cross Metathesis 939
4.4.40.47.1 Variation 1: By Molybdenum-Catalyzed Cross Metathesis 939
4.4.40.47.2 Variation 2: By Ruthenium-Catalyzed Cross Metathesis 940
4.4.40.47.3 Variation 3: By Titanium(II)-Induced Cross Metathesis 940
4.4.40.48 Method 48: Formation of 2-Substituted Allylsilanes by the Heck Reaction 941
4.4.40.49 Method 49: From [2-(Iodomethyl)allyl]trimethylsilane by Indium-Mediated Allylsilylation of Aldehydes or Ketones 943
4.4.40.50 Method 50: From [2-(Silylmethyl)allyl]lithium by a Condensation Reaction 943
4.4.40.51 Method 51: From (2-Stannylallyl)silanes by Palladium(0)-Catalyzed Cross Coupling with Acid Chlorides or Aryl Bromides 944
4.4.40.52 Method 52: From [2-(Stannylmethyl)allyl]silanes by Radical Allylsilylation with Alkyl Halides 945
4.4.40.53 Method 53: From [2-(Stannylmethyl)allyl]silanes by Thermal Allylsilylation with Acid Chlorides or Aldehydes 946
4.4.40.54 Methods 54: Additional Methods 946
Applications of Product Subclass 40 in Organic Synthesis 948
4.4.40.55 Method 55: Protodesilylation of Allylsilanes 948
4.4.40.56 Method 56: Allylation of Reactive Alkyl Halides 949
4.4.40.57 Method 57: Radical Allylation of Alkyl Halides 950
4.4.40.58 Method 58: Addition to Epoxides and Oxetanes 950
4.4.40.59 Method 59: Allylation of Aldehydes and Ketones 952
4.4.40.59.1 Variation 1: By Lewis Acid Catalyzed Allylation 952
4.4.40.59.2 Variation 2: By Lewis Base Promoted Allylation 954
4.4.40.60 Method 60: Allylation of Acetals and Ketals 955
4.4.40.61 Method 61: Acylation with Acid Chloride 956
4.4.40.62 Method 62: Reaction with Iminium Ions 957
4.4.40.63 Method 63: Epoxidation and Ring Opening 957
4.4.40.64 Method 64: Aziridination and Ring Opening 958
4.4.40.65 Method 65: Dihydroxylation of Allylsilanes 959
4.4.40.66 Method 66: Conjugate Addition to a,ß-Unsaturated Carbonyl Compounds 960
4.4.40.67 Method 67: Palladium(0)-Catalyzed [3 + 2] Cycloaddition 962
4.4.40.68 Method 68: [3 + 4] Allyl Cation Cycloaddition 963
4.4.40.69 Method 69: Hydroxycyclopentanes from [3 + 2] Annulation with a-Enones 964
4.4.40.70 Method 70: Tetrahydrofurans by [3 + 2] Annulation with Aldehydes and Ketones 965
4.4.40.71 Method 71: a-Methylenecyclopentanones from Silicon-Directed Nazarov Cyclization 965
4.4.41 Product Subclass 41: ß-Silyl Carbonyl Compounds 974
4.4.41.1 Method 1: Hydrosilylation of Alkynes and Alkenes 976
4.4.41.1.1 Variation 1: Hydrosilylation of Propargyl Alcohols, and Oxidation or Isomerization 977
4.4.41.1.2 Variation 2: Hydrosilylation and Dehydrogenation 977
4.4.41.1.3 Variation 3: Hydrosilylation--Carbonylation 978
4.4.41.2 Method 2: Silylmetalation of Alkynes and Alkenes 979
4.4.41.2.1 Variation 1: Silylmetalation of a,ß-Unsaturated Carbonyl Compounds 979
4.4.41.2.2 Variation 2: Silylmetalation and Acylation of Alkynes 981
4.4.41.3 Method 3: Electrophilic Silylation of Functionalized Three-Carbon Reagents 982
4.4.41.3.1 Variation 1: Electrophilic Silylation of Allyllithium Reagents 982
4.4.41.3.2 Variation 2: Electrophilic Silylation at C3 of Masked a,ß-Unsaturated Aldehydes and Ketones 983
4.4.41.3.3 Variation 3: Reductive Silylation of Anisole and Hydrolysis 985
4.4.41.4 Method 4: Carbonylation or Carboxylation of Vinylsilanes 986
4.4.41.5 Method 5: Trimethylsilylmethylation of Enolates and Enolate Equivalents 988
4.4.41.6 Method 6: Claisen Rearrangement of Esters of 3-Silylallyl Alcohols 989
4.4.41.7 Additional Methods 990
4.4.42 Product Subclass 42: .-Silyl Alkyl Halides, Alcohols, and Esters Thereof 994
4.4.42.1 Method 1: From Silyl Anions and Functionalized Three-Carbon Electrophiles 996
4.4.42.2 Method 2: From Silicon Electrophiles and Functionalized Three-Carbon Nucleophiles 997
4.4.42.2.1 Variation 1: Intermolecular Silylation of C,O-Dianions Derived from Functionalized Alcohols 997
4.4.42.2.2 Variation 2: Silicon Transfer in 3-Siloxy Carbanions: The Retro-[1,4]-Brook Rearrangement 998
4.4.42.3 Method 3: From a-Silylated Carbanions and Epoxides 1000
4.4.42.4 Method 4: Hydrosilylation of Allylic Compounds 1002
4.4.42.4.1 Variation 1: Hydrosilylation of Allylic Halides, Alcohols, and Esters 1002
4.4.42.4.2 Variation 2: Intramolecular Hydrosilylation of Allyloxysilanes 1003
4.4.42.5 Method 5: Coupling between Vinylsilanes and Aldehydes or Ketones 1005
4.4.42.5.1 Variation 1: Carbozirconation of Vinylsilanes 1005
4.4.42.5.2 Variation 2: Coupling Initiated by Electron Transfer 1006
4.4.42.6 Method 6: Additions to Allylsilanes 1007
4.4.42.6.1 Variation 1: Hydrometalation--Oxidation of Allylsilanes 1007
4.4.42.6.2 Variation 2: Carbometalation of Allylsilanes 1008
4.4.42.6.3 Variation 3: Free-Radical Addition to Allylsilanes 1009
4.4.42.7 Method 7: Addition of ß-Silylated Carbanions to Aldehydes and Ketones 1010
4.4.42.7.1 Variation 1: Addition of ß-Silyl Organometallic Reagents to Aldehydes and Ketones 1010
4.4.42.7.2 Variation 2: Condensation of ß-Silyl Enolates with Carbonyl Compounds 1011
Keyword Index 1020
Author Index 1050
Abbreviations 1102