Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 40a (eBook)

Volume 40a: Amines and Ammonium Salts 1
Title page 3
Imprint 5
Preface 6
Volume Editors Preface 8
Overview 10
Table of Contents 12
Introduction 30
40.1 Product Class 1: Amino Compounds 36
40.1.1 Product Subclass 1: Alkyl- and Cycloalkylamines 36
40.1.1.1 Synthesis by Reduction 52
40.1.1.1.1 Reduction of Carbonic and Carboxylic Acid Derivatives 52
40.1.1.1.1.1 Method 1: Reduction of Carbon Monoxide Gas 52
40.1.1.1.1.2 Method 2: Reduction of Carbamates 52
40.1.1.1.1.2.1 Variation 1: Reduction with Aluminum Hydrides 53
40.1.1.1.1.2.2 Variation 2: Catalytic Hydrogenation 54
40.1.1.1.1.2.3 Variations 3: Miscellaneous Reductions 56
40.1.1.1.1.3 Method 3: Reduction of Isocyanates or Isothiocyanates 57
40.1.1.1.1.4 Method 4: Reduction of Nitriles 58
40.1.1.1.1.4.1 Variation 1: Catalytic Hydrogenation 58
40.1.1.1.1.4.2 Variation 2: Reduction with Aluminum Hydrides 63
40.1.1.1.1.4.3 Variation 3: Reduction with Boranes 67
40.1.1.1.1.4.4 Variation 4: Reduction with Borohydrides 70
40.1.1.1.1.4.5 Variation 5: The Kulinkovich--de Meijere Reaction 73
40.1.1.1.1.5 Method 5: Reduction of Amides or Thioamides 74
40.1.1.1.1.5.1 Variation 1: Reduction with Aluminum Hydrides 74
40.1.1.1.1.5.2 Variation 2: Reduction with Borane Derivatives 77
40.1.1.1.1.5.3 Variation 3: Reduction with Hydrosilanes 78
40.1.1.1.1.5.4 Variation 4: Reduction of Thioamides 79
40.1.1.1.1.5.5 Variation 5: The Kulinkovich--de Meijere Reaction 80
40.1.1.1.1.6 Method 6: Reduction of Imides 83
40.1.1.1.1.7 Method 7: Reduction of Imidates and Imidoyl Chlorides 84
40.1.1.1.2 Reductive Amination of Carbonyl Compounds 94
40.1.1.1.2.1 Alkylamines from Carbonyl Compounds by Direct Reductive Amination 94
40.1.1.1.2.1.1 Method 1: Direct Reductive Amination by Catalytic Hydrogenation 95
40.1.1.1.2.1.1.1 Variation 1: Hydrogenation Using Heterogeneous Metal Catalysts 95
40.1.1.1.2.1.1.2 Variation 2: Hydrogenation Using Homogeneous Metal Complex Catalysts 96
40.1.1.1.2.1.1.3 Variation 3: Palladium-Catalyzed Transfer Hydrogenation 97
40.1.1.1.2.1.2 Method 2: Direct Reductive Amination Using Silanes as a Hydrogen Source 98
40.1.1.1.2.1.2.1 Variation 1: Using Polymethylhydrosiloxane 98
40.1.1.1.2.1.2.2 Variation 2: Using Aminohydrosilanes 98
40.1.1.1.2.1.2.3 Variation 3: Using Triethylsilane 99
40.1.1.1.2.1.3 Method 3: Direct Reductive Amination with Borohydride or Borane Reducing Agents 99
40.1.1.1.2.1.3.1 Variation 1: Using Sodium Cyanoborohydride 99
40.1.1.1.2.1.3.2 Variation 2: Using Sodium Borohydride 101
40.1.1.1.2.1.3.3 Variation 3: Using Zirconium(II) or Copper(I) Borohydrides 102
40.1.1.1.2.1.3.4 Variation 4: Using Sodium Triacyloxyborohydrides 103
40.1.1.1.2.1.3.5 Variation 5: Using Aminoboranes 103
40.1.1.1.2.2 Primary Alkylamines from Oximes and O-Alkyloximes 104
40.1.1.1.2.2.1 Primary Alkylamines from Oximes 105
40.1.1.1.2.2.1.1 Method 1: Catalytic Hydrogenation 105
40.1.1.1.2.2.1.2 Method 2: Catalytic Transfer Hydrogenation 106
40.1.1.1.2.2.1.3 Method 3: Reduction with Metallic Zinc 106
40.1.1.1.2.2.1.3.1 Variation 1: Using Zinc in the Presence of Ammonia 106
40.1.1.1.2.2.1.3.2 Variation 2: Using Zinc in the Presence of a Carboxylic Acid 107
40.1.1.1.2.2.1.4 Method 4: Reductions with Borane or Borohydrides 108
40.1.1.1.2.2.1.4.1 Variation 1: Reduction with Borane 108
40.1.1.1.2.2.1.4.2 Variation 2: Reduction with Borohydrides 108
40.1.1.1.2.2.1.5 Method 5: Reductions with Aluminum Trihydride or Hydroaluminates 109
40.1.1.1.2.2.2 Primary Alkylamines from O-Alkyloximes 110
40.1.1.1.2.3 Secondary Alkylamines from N-Alkylidenealkylamines by Reduction 111
40.1.1.1.2.3.1 Method 1: Stereorandom Reduction of N-Alkylidenealkylamines to Secondary Alkylamines 111
40.1.1.1.2.3.1.1 Variation 1: Via Transfer Hydrogenation 111
40.1.1.1.2.3.1.2 Variation 2: By Reduction with Hydrides 112
40.1.1.1.2.3.2 Method 2: Enantioselective Reduction of N-Alkylidenealkylamines to Secondary Alkylamines 113
40.1.1.1.2.4 Tertiary Alkylamines from Enamines by Reduction 114
40.1.1.1.2.4.1 Method 1: Amines from Enamines by Catalytic Hydrogenation 114
40.1.1.1.2.4.2 Method 2: Amines from Enamines by Enantioselective (Asymmetric) Catalytic Hydrogenation 115
40.1.1.1.2.4.3 Method 3: Amines from Enamines Using Other Reducing Agents 116
40.1.1.1.3 Reaction of Acetals with Organometallic Reagents 120
40.1.1.1.3.1 Method 1: Additions to N,O-Acetals 120
40.1.1.1.3.1.1 Variation 1: Addition to N,O-Acetals Incorporating a Tertiary Amine Function 120
40.1.1.1.3.1.2 Variation 2: Addition to N,O-Acetals Incorporating a Secondary Amine Function 124
40.1.1.1.3.1.3 Variation 3: Development of Asymmetric Additions to N,O-Acetals 127
40.1.1.1.3.2 Method 2: Additions to N,N-Acetals 128
40.1.1.1.3.3 Method 3: Reductive Arylation of N,O-Acetals: The Tscherniac--Einhorn Reaction 129
40.1.1.1.3.3.1 Variation 1: Asymmetric Equivalents of the Tscherniac--Einhorn Reaction 134
40.1.1.1.4 Hydroaminomethylation of Alkenes 140
40.1.1.1.4.1 Method 1: Hydroaminomethylation 140
40.1.1.1.5 Reduction of Nitrogen-Based Functional Groups 148
40.1.1.1.5.1 Reduction of Nitroalkanes 148
40.1.1.1.5.1.1 Method 1: Cathodic Reduction 149
40.1.1.1.5.1.2 Method 2: Catalytic Hydrogenation 149
40.1.1.1.5.1.3 Method 3: Transfer Hydrogenation 151
40.1.1.1.5.1.4 Method 4: Reduction Using Borohydrides and an Additional Catalyst 153
40.1.1.1.5.1.4.1 Variation 1: Using Sodium Borohydride 153
40.1.1.1.5.1.4.2 Variation 2: Using Borohydride Exchange Resin 154
40.1.1.1.5.1.4.3 Variation 3: Using Zinc(II) Borohydride--Pyridine 154
40.1.1.1.5.1.5 Method 5: Reduction Using Lithium Aluminum Hydride 154
40.1.1.1.5.1.6 Method 6: Reduction Using Aluminum Amalgam Promoted by Ultrasound 156
40.1.1.1.5.1.7 Method 7: Reduction Using Tin--Hydrochloric Acid 157
40.1.1.1.5.1.8 Method 8: Reduction Using Samarium(II) Iodide 157
40.1.1.1.5.2 Reduction of Mesoionic 2-Alkyl-1,2,3-triazines 159
40.1.1.1.5.3 Reduction of Nitrosoalkanes 160
40.1.1.1.5.4 Reduction of Alkyl Azides 160
40.1.1.1.5.4.1 Method 1: Catalytic Hydrogenation 160
40.1.1.1.5.4.2 Method 2: Transfer Hydrogenation 162
40.1.1.1.5.4.3 Method 3: Reduction Using Boranes or Boronates 164
40.1.1.1.5.4.3.1 Variation 1: Using Dichloroborane--Dimethyl Sulfide 164
40.1.1.1.5.4.3.2 Variation 2: Using Lithium Aminoborohydrides 165
40.1.1.1.5.4.3.3 Variation 3: Using Sodium Borohydride 166
40.1.1.1.5.4.3.4 Variation 4: Using Borohydride Exchange Resin--Nickel(II) Acetate 168
40.1.1.1.5.4.3.5 Variation 5: Using Zinc(II) Borohydride 168
40.1.1.1.5.4.4 Method 4: Reduction Using Lithium Aluminum Hydride 169
40.1.1.1.5.4.5 Method 5: Reduction Using Tributyltin Hydride 170
40.1.1.1.5.4.6 Method 6: Reduction Using Metals 170
40.1.1.1.5.4.7 Method 7: Reduction Using Triphenylphosphine 172
40.1.1.1.5.4.8 Method 8: Reduction Using Hydrogen Sulfide 173
40.1.1.1.5.4.9 Method 9: Reduction Using Propane-1,3-dithiol 173
40.1.1.1.5.4.10 Method 10: Reduction Using Low-Valent Metal Ion Salts 174
40.1.1.1.5.4.11 Methods 11: Miscellaneous Methods 174
40.1.1.1.5.5 Reduction of 1,2-Diazenes 174
40.1.1.1.5.6 Reduction of Hydroxylamines 175
40.1.1.1.5.7 Reduction of Amine Oxides 176
40.1.1.1.5.8 Reduction of N-Nitro and N-Nitroso Compounds 178
40.1.1.1.5.9 Reduction of Alkylhydrazines 178
40.1.1.1.5.10 Reduction of Sulfonamides 182
40.1.1.2 Synthesis by Substitution 232
40.1.1.2.1 Synthesis by Substitution of Hydrogen or Metals 232
40.1.1.2.1.1 Method 1: a-Amination of Carbonyl Compounds and Analogues 186
40.1.1.2.1.1.1 Variation 1: Amination with Azodicarboxylates 186
40.1.1.2.1.1.2 Variation 2: Amination with R2NL Compounds (L = Leaving Group) 196
40.1.1.2.1.1.3 Variation 3: Amination with Azides Followed by Reduction 199
40.1.1.2.1.1.4 Variation 4: Amination with Oxaziridines 202
40.1.1.2.1.1.5 Variation 5: Amination with 1-Chloro-1-nitroso Reagents 204
40.1.1.2.1.1.6 Variation 6: Amination with Lithium N-(tert-Butoxycarbonyl)-O-tosylhydroxyamide 205
40.1.1.2.1.1.7 Variation 7: Amination with Nitridomanganese(V) Complexes 205
40.1.1.2.1.1.8 Variations 8: Other Variations 206
40.1.1.2.1.2 Method 2: Substitution of Hydrogen Other Than the a-Hydrogen of Carbonyl Compounds 206
40.1.1.2.1.2.1 Variation 1: Amination with Azidotrimethylsilane Followed by Reduction 207
40.1.1.2.1.2.2 Variation 2: Amination of Unactivated C--H Groups with Haloamines 209
40.1.1.2.1.2.3 Variation 3: Rhodium(II)-, Ruthenium(II)-, or Manganese(III)-Catalyzed Amination 210
40.1.1.2.1.2.4 Variations 4: Miscellaneous Variations 213
40.1.1.2.1.3 Method 3: Substitution of Metal Atoms 214
40.1.1.2.1.3.1 Variation 1: Substitution of Boron 215
40.1.1.2.1.3.2 Variation 2: Substitution of Zinc 216
40.1.1.2.1.3.3 Variation 3: Substitution of Copper 219
40.1.1.2.1.3.4 Variation 4: Substitution of Magnesium 220
40.1.1.2.1.3.5 Variation 5: Substitution of Lithium 224
40.1.1.2.1.3.6 Variation 6: Substitution of Other Metal Atoms 226
40.1.1.2.2 Substitution of Carbon Functionalities via Solvolysis 232
40.1.1.2.2.1 Method 1: Substitution of Carbamates 232
40.1.1.2.2.1.1 Variation 1: Cleavage by Nucleophilic Substitution 232
40.1.1.2.2.1.2 Variation 2: Cleavage by Protic or Lewis Acids 235
40.1.1.2.2.1.3 Variation 3: Cleavage by Base-Induced ß-Elimination 239
40.1.1.2.2.1.4 Variation 4: Cleavage by Remote Attack of Bases or Nucleophiles at the Carbamate Group 242
40.1.1.2.2.2 Method 2: Substitution of Carboxylic Acid N-Derivatives 248
40.1.1.2.2.2.1 Variation 1: Acyclic Carboxylic Acid N-Derivatives 248
40.1.1.2.2.2.2 Variation 2: Cyclic Carboxylic Acid N-Derivatives (Cyclic Imide Derivatives) 255
40.1.1.2.2.2.3 Variation 3: Amidines 258
40.1.1.2.3 Substitution of Sulfur or Phosphorus Functionalities 262
40.1.1.2.3.1 Method 1: Cleavage of Sulfonic, Sulfinic, and Sulfenic Acid N-Derivatives 262
40.1.1.2.3.2 Method 2: Cleavage of Phosphoric and Phosphinic Acid Amides 266
40.1.1.3 Synthesis by Addition Reactions 270
40.1.1.3.1 Hydroamination 270
40.1.1.3.1.1 Method 1: Hydroamination of Alkenes 270
40.1.1.3.1.1.1 Variation 1: Catalysis by Acids 270
40.1.1.3.1.1.2 Variation 2: Catalysis by Bases 272
40.1.1.3.1.1.3 Variation 3: Catalysis by Calcium Complexes 274
40.1.1.3.1.1.4 Variation 4: Catalysis by Rare Earth Metal Complexes 275
40.1.1.3.1.1.5 Variation 5: Catalysis by Actinide Complexes 285
40.1.1.3.1.1.6 Variation 6: Catalysis by Group 4 Metal Complexes 286
40.1.1.3.1.1.7 Variation 7: Catalysis by Group 8 Metal Complexes 288
40.1.1.3.1.1.8 Variation 8: Catalysis by Group 9 Metal Complexes 289
40.1.1.3.1.1.9 Variation 9: Catalysis by Group 10 Metal Complexes 290
40.1.1.3.1.1.10 Variation 10: Catalysis by Group 11 Metal Complexes 292
40.1.1.3.1.1.11 Variation 11: Catalysis by Group 12 Metal Complexes 293
40.1.1.3.1.2 Method 2: Hydroamination of Vinylarenes 293
40.1.1.3.1.2.1 Variation 1: Catalysis by Acids 293
40.1.1.3.1.2.2 Variation 2: Catalysis by Bases 294
40.1.1.3.1.2.3 Variation 3: Catalysis by Rare Earth Metal Complexes 295
40.1.1.3.1.2.4 Variation 4: Catalysis by Hafnium Complexes 297
40.1.1.3.1.2.5 Variation 5: Catalysis by Ruthenium Complexes 298
40.1.1.3.1.2.6 Variation 6: Catalysis by Rhodium Complexes 299
40.1.1.3.1.2.7 Variation 7: Catalysis by Palladium or Platinum Complexes 301
40.1.1.3.1.2.8 Variation 8: Catalysis by Copper Complexes 302
40.1.1.3.1.2.9 Variation 9: Catalysis by Bismuth Complexes 303
40.1.1.3.1.2.10 Variation 10: Catalysis by N-Bromosuccinimide 303
40.1.1.3.1.2.11 Variation 11: Photoamination of Vinylarenes 304
40.1.1.3.1.3 Method 3: Hydroamination of 1,3-Dienes 304
40.1.1.3.1.3.1 Variation 1: Catalysis by Acids 305
40.1.1.3.1.3.2 Variation 2: Catalysis by Bases 305
40.1.1.3.1.3.3 Variation 3: Catalysis by Rare Earth Metal Complexes 306
40.1.1.3.1.3.4 Variation 4: Catalysis by Group 10 Metal Complexes 307
40.1.1.3.1.3.5 Variation 5: Catalysis by Gold Complexes 308
40.1.1.3.1.3.6 Variation 6: Catalysis by Bismuth Complexes 308
40.1.1.3.1.3.7 Variation 7: Photoamination of 1,3-Dienes 309
40.1.1.3.1.4 Method 4: Hydroamination of Cyclohepta-1,3,5-triene 309
40.1.1.3.1.5 Method 5: Hydroamination of Allenes 310
40.1.1.3.1.5.1 Variation 1: Catalysis by Rare Earth Metal Complexes 310
40.1.1.3.1.5.2 Variation 2: Catalysis by Titanium or Zirconium Complexes 311
40.1.1.3.1.5.3 Variation 3: Catalysis by Ruthenium Complexes 312
40.1.1.3.1.5.4 Variation 4: Catalysis by Palladium Complexes 313
40.1.1.3.1.5.5 Variation 5: Catalysis by Gold or Silver Complexes 315
40.1.1.3.1.6 Method 6: Hydroamination of Allenes and Subsequent Reduction 316
40.1.1.3.1.7 Method 7: Hydroamination of Alkynes 317
40.1.1.3.1.8 Method 8: Hydroamination of Alkynes and Subsequent Reduction 318
40.1.1.3.1.8.1 Variation 1: Catalysis by Rare Earth Metal Complexes 318
40.1.1.3.1.8.2 Variation 2: Catalysis by Group 4 Metal Complexes 319
40.1.1.3.1.8.3 Variation 3: Catalysis by Iridium Complexes 321
40.1.1.3.1.8.4 Variation 4: Catalysis by Silver Complexes 322
40.1.1.3.1.9 Method 9: Hydroamination of Alkynes and Nucleophilic Addition 322
40.1.1.3.1.10 Method 10: Hydroamination of Enynes 323
40.1.1.3.1.11 Method 11: Hydroamination of Methylenecyclopropanes 324
40.1.1.3.1.11.1 Variation 1: Catalysis by Rare Earth Metal Complexes 324
40.1.1.3.1.11.2 Variation 2: Catalysis by Palladium Complexes 325
40.1.1.3.1.11.3 Variation 3: Catalysis by Gold Complexes 325
40.1.1.3.1.12 Method 12: Hydroamination of Cyclopropenes 326
40.1.1.3.1.13 Method 13: Hydroamination of Cyclopropanes 326
40.1.1.3.1.13.1 Variation 1: Catalysis by Palladium Complexes 326
40.1.1.3.1.13.2 Variation 2: Photoamination of Cyclopropanes 327
40.1.1.3.1.14 Method 14: Hydroamination of Aromatic Compounds 327
40.1.1.3.2 Addition of Carbanions to Azomethines 334
40.1.1.3.2.1 Azomethines for Asymmetric Addition of Carbanions 334
40.1.1.3.2.1.1 Method 1: Use of N-(1-Phenylethyl)imines 334
40.1.1.3.2.1.2 Method 2: Use of N-Sulfinylimines 336
40.1.1.3.2.1.3 Method 3: Use of SAMP and RAMP Hydrazones 337
40.1.1.3.2.1.4 Method 4: Use of Chiral Acylhydrazones 338
40.1.1.3.2.1.5 Method 5: Use of Chiral Oxime O-Ethers 339
40.1.1.3.2.1.6 Method 6: Use of Chiral Reagents and Catalysts 340
40.1.1.3.2.2 Addition of Organometallic or Radical Reagents to Azomethines 342
40.1.1.3.2.2.1 Method 1: Addition of Allylmetal Reagents 342
40.1.1.3.2.2.1.1 Variation 1: Of Allyllithium and Allylmagnesium Reagents 343
40.1.1.3.2.2.1.2 Variation 2: Of Allylboranes 346
40.1.1.3.2.2.1.3 Variation 3: Of Allylstannanes 348
40.1.1.3.2.2.1.4 Variation 4: Of Allylsilanes 351
40.1.1.3.2.2.1.5 Variation 5: Of Other Allylic Reagents 354
40.1.1.3.2.2.2 Method 2: Addition of Alkyl- and Arylmetal Reagents 355
40.1.1.3.2.2.2.1 Variation 1: Of Organolithiums and Grignard Reagents 355
40.1.1.3.2.2.2.2 Variation 2: Of Organozinc Reagents 356
40.1.1.3.2.2.2.3 Variation 3: Of Organocerium Reagents 358
40.1.1.3.2.2.2.4 Variation 4: Of Organotransition Metal Species 360
40.1.1.3.2.2.2.5 Variation 5: Of Other Organometallic Reagents 362
40.1.1.3.2.2.3 Method 3: Radical Alkyl Additions 362
40.1.1.3.3 Pericyclic Reactions Involving C==N Units 372
40.1.1.3.3.1 Method 1: Cycloaddition Reactions of N-Acylimines 372
40.1.1.3.3.2 Method 2: Cycloaddition Reactions of N-(Alkoxycarbonyl)imines 374
40.1.1.3.3.2.1 Variation 1: Lewis Acid Mediated Cycloaddition of Biscarbamates 375
40.1.1.3.3.2.2 Variation 2: Enantioselective Catalytic Cycloaddition 376
40.1.1.3.3.3 Method 3: Cycloaddition Reactions of N-Sulfonylimines or N-Phosphorylimines 377
40.1.1.3.3.3.1 Variation 1: Diastereoselective Cycloaddition Reactions of N-Tosylimines 378
40.1.1.3.3.3.2 Variation 2: Enantioselective Catalytic Cycloaddition Reactions of N-Tosylimines 379
40.1.1.3.3.4 Method 4: Cycloaddition Reactions of N-Alkylimines, N-Arylimines, or Their Salts 380
40.1.1.3.3.4.1 Variation 1: Acid-Catalyzed Imino-Diels--Alder Reactions in Aqueous Media 381
40.1.1.3.3.4.2 Variation 2: Diastereoselective Cycloaddition Reactions of N-Alkyl- or N-Arylimines 382
40.1.1.3.3.4.3 Variation 3: Enantioselective Catalytic Cycloaddition Reactions of Alkylated and Arylated Imines 385
40.1.1.3.3.5 Method 5: Cycloaddition Reactions of C-Heteroatom-Substituted Imines 386
40.1.1.4 Synthesis by Rearrangement 394
40.1.1.4.1 Rearrangements from Nitrogen to Carbon 394
40.1.1.4.1.1 Method 1: Stevens and Sommelet--Hauser Rearrangements 394
40.1.1.4.1.2 Method 2: [2,3]-Aza-Wittig and Related Sigmatropic Rearrangements 408
40.1.1.4.1.2.1 Variation 1: [2.3]-Aza-Wittig Rearrangements 408
40.1.1.4.1.2.2 Variation 2: Rearrangements Involving Compounds Containing Sulfur or Selenium 409
40.1.1.4.1.3 Method 3: Rearrangements of Phenylhydrazines and Hydrazobenzenes 411
40.1.1.4.1.4 Method 4: Overman Rearrangement (Aza-Oxa-Cope Rearrangement) 411
40.1.1.4.1.5 Method 5: Rearrangements of N-Substituted Amines 417
40.1.1.4.1.5.1 Variation 1: Fischer--Hepp Rearrangement 417
40.1.1.4.1.5.2 Variation 2: Hofmann--Martius Rearrangement 418
40.1.1.4.1.5.3 Variation 3: Reilly--Hickinbottom and Orton Rearrangements 420
40.1.1.4.1.5.4 Variation 4: Bamberger Rearrangement 420
40.1.1.4.1.5.5 Variation 5: Hofmann--Löffler--Freytag Rearrangement 421
40.1.1.4.2 Rearrangements from Carbon to Nitrogen 422
40.1.1.4.2.1 Method 1: Stieglitz Rearrangements 422
40.1.1.4.2.2 Method 2: Beckmann Rearrangement 422
40.1.1.4.2.3 Method 3: Neber Rearrangement 423
40.1.1.4.2.4 Method 4: Hofmann, Curtius, Schmidt, and Lossen Rearrangements 424
40.1.1.4.2.4.1 Variation 1: Hofmann Rearrangement 425
40.1.1.4.2.4.2 Variation 2: Lossen Rearrangement 430
40.1.1.4.2.4.3 Variation 3: Curtius Rearrangement 433
40.1.1.4.2.4.4 Variation 4: Schmidt Rearrangement 440
40.1.1.5 Synthesis from Other Amino Compounds 448
40.1.1.5.1 Resolution of Chiral Amines 448
40.1.1.5.1.1 Method 1: Resolution by Diastereomeric Crystallization 448
40.1.1.5.1.2 Method 2: Kinetic Resolution 450
40.1.1.5.1.2.1 Variation 1: Enzymatic Kinetic Resolution 450
40.1.1.5.1.2.2 Variation 2: Dynamic Kinetic Resolution Using Enzymes 454
40.1.1.5.1.2.3 Variation 3: Nonenzymatic Kinetic Resolution 456
40.1.1.5.1.3 Method 3: Analytical and Preparative Chromatographic Separation 457
40.1.1.5.1.4 Method 4: Analysis and Separation of Diastereomeric Amine Derivatives 458
40.1.1.5.1.4.1 Variation 1: Using Chiral Solvating Agents 459
40.1.1.5.1.4.2 Variation 2: Using Chiral Derivatizing Agents 460
40.1.1.5.2 The Mannich Reaction 464
40.1.1.5.2.1 Direct Organocatalytic Enantioselective Mannich Reaction 464
40.1.1.5.2.1.1 Method 1: a-Aminoalkylation of Ketones 465
40.1.1.5.2.1.1.1 Variation 1: Proline-Catalyzed Aminoalkylation of Aliphatic Ketones 465
40.1.1.5.2.1.1.2 Variation 2: Chiral Brønsted Acid Catalyzed Aminoalkylation of Ketones 467
40.1.1.5.2.1.1.3 Variation 3: Aminoalkylation under High Pressure 468
40.1.1.5.2.1.2 Method 2: a-Aminomethylation of Ketones 469
40.1.1.5.2.1.2.1 Variation 1: Proline-Catalyzed a-Aminomethylation 469
40.1.1.5.2.1.2.2 Variation 2: a-Aminomethylation of Ketones under Microwave Irradiation 470
40.1.1.5.2.1.3 Method 3: a-Aminoalkylation of Hydroxy and Protected Amino Ketones 471
40.1.1.5.2.1.3.1 Variation 1: Synthesis of syn-1,2-Amino Alcohols 471
40.1.1.5.2.1.3.2 Variation 2: Synthesis of Protected Amino Sugars by Direct Mannich Reaction 472
40.1.1.5.2.1.3.3 Variation 3: Synthesis of Chiral syn-1,2-Diamines 474
40.1.1.5.2.1.3.4 Variation 4: Synthesis of anti-1,2-Amino Alcohols 475
40.1.1.5.2.1.4 Method 4: Asymmetric Cross-Mannich Reaction of Aldehydes 476
40.1.1.5.2.1.4.1 Variation 1: Stereoselective Synthesis of ß-Amino Alcohols 477
40.1.1.5.2.1.4.2 Variation 2: Self-Mannich Reaction of Aliphatic and a-Hydroxy Aldehydes 478
40.1.1.5.2.1.4.3 Variation 3: One-Pot Direct Synthesis of ß-Formyl-a-amino Acids 478
40.1.1.5.2.2 Indirect Organocatalytic Enantioselective Mannich Reaction with Preformed Reagents 480
40.1.1.5.2.2.1 Method 1: ß-Amino Carbonyl Derivatives from Reactions of N-(tert-Butoxycarbonyl)-Protected Imines 480
40.1.1.5.2.2.1.1 Variation 1: Proline-Catalyzed Addition of Aldehydes or Ketones 480
40.1.1.5.2.2.1.2 Variation 2: Chiral Brønsted Acid Catalyzed Reaction of N-(tert-Butoxycarbonyl)-Protected Aldimines 481
40.1.1.5.2.2.2 Method 2: a-Amino Acids by syn-Selective Synthesis 482
40.1.1.5.2.2.2.1 Variation 1: Proline-Catalyzed Reaction of Ketones with N-(4-Methoxyphenyl)-Protected a-Imino Ethyl Glyoxylate 482
40.1.1.5.2.2.2.2 Variation 2: 5-(Pyrrolidin-2-yl)tetrazole-Catalyzed Reaction of Ketones with N-(4-Methoxyphenyl)-Protected Imines 483
40.1.1.5.2.2.2.3 Variation 3: Reaction of Enolizable Aldehydes with N-(4-Methoxyphenyl)-Protected a-Imines 484
40.1.1.5.2.2.3 Method 3: a-Amino Acids by anti-Selective Synthesis 485
40.1.1.5.2.2.3.1 Variation 1: Reaction of Enolizable Aldehydes Catalyzed by a Chiral Amino Sulfonamide 485
40.1.1.5.2.2.3.2 Variation 2: Reaction of Enolizable Aldehydes Catalyzed by a Chiral Pyrrolidine-Based Amino Sulfonamide 486
40.1.1.5.2.2.3.3 Variation 3: Reaction of Enolizable Aldehydes Catalyzed by Amino Acid Derivatives 487
40.1.1.5.2.2.3.4 Variation 4: anti-Mannich Reactions of Unmodified Ketones 488
40.1.1.5.2.2.3.5 Variation 5: Synthesis of Optically Active Quaternary a-Amino Acid Derivatives 489
40.1.1.5.2.2.4 Method 4: ß-Amino Acids by Indirect Mannich Reaction of Ketene Silyl Acetals with Protected Imines 490
40.1.1.5.2.2.4.1 Variation 1: Chiral-Thiourea-Catalyzed Addition of Ketene Silyl Acetals to N-(tert-Butoxycarbonyl)aldimines 490
40.1.1.5.2.2.4.2 Variation 2: Chiral Brønsted Acid Catalyzed Reaction of Aldimines with Ketene Silyl Acetals 491
40.1.1.5.2.2.5 Method 5: ß-Amino Acids by Addition of CH-Acidic 1,3-Dicarbonyl Compounds to Protected Imines 493
40.1.1.5.2.2.5.1 Variation 1: Enantioselective Addition of Malonate to N-(tert-Butoxy-carbonyl)-Protected Aromatic and Aliphatic Aldimines 493
40.1.1.5.2.2.5.2 Variation 2: Addition of ß-Oxo Esters to Protected Imines Catalyzed by Cinchona Alkaloids 493
40.1.1.5.2.2.5.3 Variation 3: Stereoselective Synthesis of a,ß-Diamino Acids Using a Chiral Phase-Transfer Catalyst 494
40.1.1.5.2.3 Metal-Catalyzed Asymmetric Mannich Reaction 496
40.1.1.5.2.3.1 Method 1: Synthesis Using Silyl Enol Ethers and Ketene Silyl Acetals as Nucleophiles 496
40.1.1.5.2.3.1.1 Variation 1: Enantio- and Diastereoselective Synthesis of ß-Amino Carbonyl Compounds 497
40.1.1.5.2.3.1.2 Variation 2: Enantio- and Diastereoselective Synthesis of ß-Amino Ketones in Water 498
40.1.1.5.2.3.1.3 Variation 3: Enantioselective Synthesis of ß-Amino Esters 499
40.1.1.5.2.3.2 Method 2: Synthesis of anti- or syn-ß-Amino-a-hydroxy Ketones 501
40.1.1.5.2.3.2.1 Variation 1: Metal--1,1'-Binaphthalene-2,2'-diol Complexes as Catalyst 501
40.1.1.5.2.3.2.2 Variation 2: Dinuclear Zinc Complexes as Catalyst 502
40.1.1.5.3 Modification of Mannich Adducts 508
40.1.1.5.3.1 Modification of the Amino Group 508
40.1.1.5.3.1.1 Method 1: Deprotection of the N-(tert-Butoxycarbonyl) Group 508
40.1.1.5.3.1.2 Method 2: Deprotection of N-(4-Hydroxyphenyl), N-(4-Methoxyphenyl), and N-(2-Methoxyphenyl) Groups 509
40.1.1.5.3.1.3 Method 3: Deprotection of N-(Diarylphosphoryl) Groups 510
40.1.1.5.3.1.4 Method 4: Deprotection of N-(Arylsulfonyl) Groups 510
40.1.1.5.3.1.5 Method 5: Deprotection of the N-[(R)-2-Hydroxy-1-phenylethyl] Group 511
40.1.1.5.3.1.6 Method 6: Acylation Using Triphosgene 511
40.1.1.5.3.1.7 Method 7: Guanidinylation and the Synthesis of Capreomycidine 513
40.1.1.5.3.1.8 Method 8: Synthesis of Enantioenriched Dihydropyrimidinones 514
40.1.1.5.3.2 Modification of the Carbonyl Group 515
40.1.1.5.3.2.1 Method 1: Enantioselective Synthesis of ß2-Amino Acid Derivatives 515
40.1.1.5.3.2.2 Method 2: Enantioselective Synthesis of ß2,3-Amino Acid Derivatives 517
40.1.1.5.3.2.3 Method 3: Baeyer--Villiger Oxidation 518
40.1.1.5.3.2.4 Method 4: Diastereoselective Reduction: Synthesis of (+)-Polyoxamic Acid 518
40.1.1.5.3.2.5 Method 5: Synthesis of ß-Lactams 520
40.1.1.5.3.2.6 Method 6: Palladium-Catalyzed Carbonylation: Synthesis of (±)-Gelsemine 521
40.1.1.5.3.2.7 Method 7: Synthesis of Peptides: Synthesis of Azumamide A 522
40.1.1.5.3.3 Reduction of the Carbonyl Group and Imines 523
40.1.1.5.3.3.1 Method 1: Enantioselective Synthesis of 1,3-Amino Alcohols: Synthesis of HPA-12 524
40.1.1.5.3.3.2 Method 2: Enantioselective Synthesis of 1,3-Amino Alcohols: Synthesis of (--)-Sedamine 524
40.1.1.5.3.3.3 Method 3: Enantioselective Synthesis of 1,3-Diamines 526
40.1.1.5.4 Substitution on the Amine Nitrogen 530
40.1.1.5.4.1 Dealkylation Reactions of Amines 530
40.1.1.5.4.1.1 Method 1: The von Braun Reaction with Cyanogen Bromide 530
40.1.1.5.4.1.2 Method 2: Dealkylation by Acylation 533
40.1.1.5.4.1.3 Method 3: Nitrosative Dealkylation Reactions 538
40.1.1.5.4.1.4 Method 4: Dealkylation by Transamination 538
40.1.1.5.4.1.5 Method 5: Acid-Mediated Dealkylation 540
40.1.1.5.4.1.6 Method 6: Photolytic Dealkylation 541
40.1.1.5.4.1.7 Method 7: Cleavage of the C--N Bond Using Selenols 541
40.1.1.5.4.1.8 Method 8: Cleavage of the C--N Bond Using Wilkinson's Catalyst 542
40.1.1.5.4.1.9 Method 9: Reductive Cleavage of the C--N Bond 543
40.1.1.5.4.2 Dealkylation Reactions of Ammonium Salts 544
40.1.1.5.4.2.1 Method 1: Thermolytic Dealkylation 544
40.1.1.5.4.2.2 Method 2: The Hofmann Elimination Reaction 544
40.1.1.5.4.2.3 Method 3: Dealkylation with Ammonia, Amines, 2-Aminoethanol, or Other Bases 547
40.1.1.5.4.2.4 Method 4: Dealkylation Reactions with Alkali Metals or Metal Hydrides 548
40.1.1.5.4.2.5 Method 5: Dealkylation Reactions Using Sulfur Nucleophiles 549
40.1.1.5.4.2.6 Method 6: Electrolytic Methods of Cleavage 552
40.1.1.5.4.3 Replacement of Halogen Functionalities 552
40.1.1.5.4.3.1 Method 1: Reaction of Ammonia with Alkyl Halides 552
40.1.1.5.4.3.2 Method 2: Reactions of Primary, Secondary, or Tertiary Amines with Alkyl Halides 555
40.1.1.5.4.3.3 Method 3: Reactions of Alkali Metal Amide Salts 560
40.1.1.5.4.3.4 Method 4: The Gabriel Synthesis and Related Reactions of Carboxylic Acid Derivatives 560
40.1.1.5.4.3.5 Method 5: Reactions of Nitrogen-Containing Derivatives of Carbonic Acid 563
40.1.1.5.4.3.6 Method 6: Reactions with Hexamethylenetetramine 565
40.1.1.5.4.3.7 Method 7: Reaction with Sulfonamides 567
40.1.1.5.4.3.8 Method 8: Reaction with Amides of Phosphorus Acids 568
40.1.1.5.4.3.9 Method 9: Reactions of Alkyl Halides with Silylamines and Silylamides 571
40.1.1.5.4.3.10 Method 10: Intra- and Intermolecular Cyclization Reactions 572
40.1.1.5.4.3.11 Method 11: Reactions of Haloamines 576
40.1.1.5.4.4 Replacement of Oxygen Functionalities 577
40.1.1.5.4.4.1 Method 1: Reactions of Ammonia with Alcoholic Hydroxy Groups 577
40.1.1.5.4.4.2 Method 2: Reactions of Primary or Secondary Amines with Alcoholic Hydroxy Groups 579
40.1.1.5.4.4.3 Method 3: The Mitsunobu and Related Reactions 581
40.1.1.5.4.4.4 Method 4: Intermolecular Schmidt Reaction 588
40.1.1.5.4.4.5 Method 5: Reactions of Ammonia and Amines with Ethers 589
40.1.1.5.4.4.6 Method 6: Alkylation with Sulfates 594
40.1.1.5.4.4.7 Method 7: Alkylation with Sulfonates 595
40.1.1.5.4.4.8 Method 8: Alkylation with Nitrates 598
40.1.1.5.4.4.9 Method 9: Reactions with O--P Groups 598
40.1.1.5.4.4.10 Method 10: Reactions with O--Si Groups 598
40.1.2 Product Subclass 2: Propargylic Amines 608
40.1.2.1 Synthesis of Product Subclass 2 608
40.1.2.1.1 Method 1: Ethynylations of Azomethines 608
40.1.2.1.1.1 Variation 1: Catalyzed by Iridium(I) Complexes 608
40.1.2.1.1.2 Variation 2: Catalyzed by a Copper(I)--pybox Complex 609
40.1.2.1.2 Method 2: Three-Component Coupling of an Aldehyde, an Alkyne, and an Amine 609
40.1.2.1.2.1 Variation 1: Catalyzed by Copper(I) Salts 609
40.1.2.1.2.2 Variation 2: Catalyzed by Copper(I) Bromide/Ruthenium(III) Chloride 611
40.1.2.1.2.3 Variation 3: Catalyzed by Gold(III) Bromide 611
40.1.2.1.2.4 Variation 4: Catalyzed by Silver(I) Salts 612
40.1.2.1.3 Method 3: Copper-Catalyzed Cross-Dehydrogenative Coupling 613
40.1.3 Product Subclass 3: Allylic Amines 616
40.1.3.1 Synthesis of Product Subclass 3 616
40.1.3.1.1 Method 1: Synthesis by Substitution of Hydrogen 616
40.1.3.1.1.1 Variation 1: By Ene-Type Reaction 616
40.1.3.1.1.2 Variation 2: Allylic Amination via the Insertion of Nitrenes 619
40.1.3.1.2 Method 2: Synthesis by the Substitution of a Halogen or a Leaving Group 620
40.1.3.1.2.1 Variation 1: By Palladium-Catalyzed Allylic Substitution 620
40.1.3.1.3 Method 3: Synthesis by Addition 623
40.1.3.1.3.1 Variation 1: Of Nitrogen Reagents to Vinylphosphonium Salts 623
40.1.3.1.3.2 Variation 2: By Aza-Baylis--Hillman Reaction 626
40.1.3.1.3.3 Variation 3: By Aza-Diels--Alder Reaction 630
40.1.3.1.4 Method 4: Synthesis by Rearrangement 635
40.1.3.1.4.1 Variation 1: Of Aziridines 635
40.1.3.1.4.2 Variation 2: By Aza-Oxa-Cope Rearrangement 635
40.1.3.1.4.3 Variation 3: By [2,3]-Sigmatropic Rearrangement 638
40.1.4 Product Subclass 4: n-Nitrogen- or n-Phosphorus-Functionalized Alkylamines (n =2) 644
40.1.4.1 Synthesis of Product Subclass 4 644
40.1.4.1.1 Synthesis by Addition across C==C Bonds 644
40.1.4.1.1.1 Method 1: Amination of 1,3-Dienes 644
40.1.4.1.1.1.1 Variation 1: 1,2-Diamination 644
40.1.4.1.1.1.2 Variation 2: 1,4-Diamination 644
40.1.4.1.1.2 Method 2: Amination of Alkenes 645
40.1.4.1.1.2.1 Variation 1: Direct Addition of Nitrogen Compounds 645
40.1.4.1.1.2.2 Variation 2: a,.-Diamines by Carbonylative Bis(hydroaminomethylation) of a,.-Dialkenes 648
40.1.4.1.1.2.3 Variation 3: 1,2-Diamines via 4,5-Dihydroimidazoles 649
40.1.4.1.2 Synthesis by Addition across C--N Bonds 650
40.1.4.1.2.1 Method 1: Ring Opening of Aziridines 650
40.1.4.1.2.1.1 Variation 1: Addition of Amines 650
40.1.4.1.2.1.2 Variation 2: Addition of Azides 651
40.1.4.1.2.2 Method 2: Ring Opening of Azetidines 654
40.1.4.1.2.3 Method 3: Synthesis by Coupling of Nitrogen Compounds 654
40.1.4.1.2.3.1 Variation 1: Coupling of Imines 654
40.1.4.1.2.3.2 Variation 2: Coupling of Amines 658
40.1.4.1.2.3.3 Variation 3: Coupling of Nitriles 659
40.1.4.1.3 Synthesis by Addition across C--C Bonds 659
40.1.4.1.3.1 Method 1: Amine Addition to Epoxides 659
40.1.4.1.4 Synthesis by Rearrangement 660
40.1.4.1.4.1 Method 1: 1,2-Diamines via [2,3]-Sigmatropic Rearrangement 660
40.1.4.1.4.1.1 Variation 1: Rearrangement of Sulfur Imides 660
40.1.4.1.4.1.2 Variation 2: Rearrangement of Selenium Imides 661
40.1.4.1.4.2 Method 2: 1,2-Diamines via [3,3]-Sigmatropic Rearrangement 662
40.1.4.1.5 Synthesis by Reduction of a-Amino Amides 662
40.1.4.1.6 Synthesis of 2-Nitroamines 663
40.1.4.1.6.1 Method 1: Synthesis by Nitro-Mannich Reaction 663
40.1.4.1.6.2 Method 2: Synthesis by Addition of Nitrogen Compounds to Alkenes 665
40.1.4.1.7 Synthesis of (Aminoalkyl)phosphines 666
40.1.4.1.7.1 Method 1: Synthesis by Amination of Unsaturated Phosphines 666
40.1.4.1.7.2 Method 2: Synthesis by Addition of Phosphines to Unsaturated Amines 666
40.1.4.2 Applications of Product Subclass 4 in Organic Synthesis 667
40.1.5 Product Subclass 5: Aziridines 672
40.1.5.1 Synthesis of Product Subclass 5 672
40.1.5.1.1 Method 1: Addition to Alkenes 672
40.1.5.1.1.1 Variation 1: Addition of Nitrenes 672
40.1.5.1.1.2 Variation 2: Addition of Metal Nitrenoids 677
40.1.5.1.1.3 Variation 3: Addition of Azides 687
40.1.5.1.1.4 Variation 4: Addition of Hydrazine Derivatives 688
40.1.5.1.1.5 Variation 5: Addition of Hydroxylamine Derivatives 689
40.1.5.1.2 Method 2: Addition to Imines 691
40.1.5.1.2.1 Variation 1: Addition of Carbenes 691
40.1.5.1.2.2 Variation 2: Addition of Metal Carbenoids 692
40.1.5.1.2.3 Variation 3: Via Nucleophilic Attack of Anions of 2-Halo and 2-Pseudohalo Esters 696
40.1.5.1.2.4 Variation 4: Cyclization of Azomethine Ylides 704
40.1.5.1.2.5 Variation 5: Addition of Nucleophiles to Azirines 705
40.1.5.1.2.6 Variation 6: Cycloaddition of Azirines 712
40.1.5.1.3 Method 3: Addition to Aldehydes Using Guanidinium Ylides 714
40.1.5.1.4 Method 4: Cyclization Reactions 715
40.1.5.1.4.1 Variation 1: Cyclization of 2-Haloalkanamines 715
40.1.5.1.4.2 Variation 2: Cyclization of 2-Aminoalkanols 720
40.1.5.1.4.3 Variation 3: Cyclization of 2-Azidoalkanols 727
40.1.5.1.4.4 Variation 4: Via Cyclic Sulfates 729
40.1.5.1.4.5 Variation 5: Cyclization of 1-Azido-2-haloalkanes 730
40.1.5.1.4.6 Variation 6: Cyclization of Allenyl-Substituted Amines 731
40.1.5.1.4.7 Variation 7: Cyclization of (2-Bromoallyl)amines 732
40.1.5.1.5 Method 5: Ring Contraction of 4,5-Dihydro-1H-1,2,3-triazoles 732
40.1.5.1.6 Method 6: Substituent Modification 734
40.1.5.1.6.1 Variation 1: Substitution of Existing Substituents 734
40.1.5.1.6.2 Variation 2: Of Hydrogen: Deprotonation 736
40.1.5.2 Applications of Product Subclass 5 in Organic Synthesis 741
40.1.5.2.1 Ring Opening of Saturated Aziridines 741
40.1.5.2.1.1 Method 1: Ring Opening with Hydrogen 742
40.1.5.2.1.1.1 Variation 1: Hydrogenolysis 742
40.1.5.2.1.1.2 Variation 2: By Complex Hydrides 744
40.1.5.2.1.1.3 Variation 3: By Metal Reducing Agents 745
40.1.5.2.1.2 Method 2: Ring Opening Using Oxygen Nucleophiles 746
40.1.5.2.1.2.1 Variation 1: By Water 746
40.1.5.2.1.2.2 Variation 2: By Alcohols 748
40.1.5.2.1.2.3 Variation 3: By Carboxylates 749
40.1.5.2.1.2.4 Variation 4: Intramolecular Ring Opening by Oxygen Nucleophiles 750
40.1.5.2.1.3 Method 3: Ring Opening Using Nitrogen Nucleophiles 753
40.1.5.2.1.3.1 Variation 1: By Aliphatic Amines 753
40.1.5.2.1.3.2 Variation 2: By Aromatic Amines 754
40.1.5.2.1.3.3 Variation 3: By Azide 755
40.1.5.2.1.3.4 Variation 4: By Hydroxylamine 758
40.1.5.2.1.3.5 Variation 5: Intramolecular Ring Opening by Nitrogen Nucleophiles 759
40.1.5.2.1.4 Method 4: Ring Opening Using Sulfur Nucleophiles 759
40.1.5.2.1.5 Method 5: Ring Opening Using Halogen Nucleophiles 761
40.1.5.2.1.6 Method 6: Ring Opening Using Carbon Nucleophiles 764
40.1.5.2.1.6.1 Variation 1: By Carbanions 764
40.1.5.2.1.6.2 Variation 2: By Enolates 770
40.1.5.2.1.6.3 Variation 3: By Arenes 771
40.1.5.2.1.6.4 Variation 4: By Cyanide 773
40.1.5.2.1.7 Method 7: Ring Opening by Deprotonation 774
40.1.5.2.1.7.1 Variation 1: Elimination Reactions 774
40.1.5.2.1.7.2 Variation 2: Rearrangement Reactions 775
40.1.5.2.1.8 Method 8: Ring Opening Using Lewis Acids 776
40.1.5.2.1.9 Method 9: Ring Opening by Thermolysis 778
40.1.5.2.1.10 Method 10: Carbonylative Ring Expansion 779
40.1.5.2.2 Ring Opening of Alkenyl- and Alkynylaziridines 780
40.1.5.2.2.1 Method 1: Ring Opening by Hydride 780
40.1.5.2.2.2 Method 2: Ring Opening by Oxygen Nucleophiles 781
40.1.5.2.2.2.1 Variation 1: By Water 781
40.1.5.2.2.2.2 Variation 2: By Carboxylates 782
40.1.5.2.2.2.3 Variation 3: Intramolecular Ring Opening by Oxygen Nucleophiles 782
40.1.5.2.2.3 Method 3: Ring Opening Using Amino Nucleophiles 783
40.1.5.2.2.4 Method 4: Ring Opening Using Halogen Nucleophiles 784
40.1.5.2.2.5 Method 5: Ring Opening Using Carbon Nucleophiles 784
40.1.5.2.2.5.1 Variation 1: By Carbanions 784
40.1.5.2.2.5.2 Variation 2: With Palladium Catalysis 787
40.1.5.2.2.6 Method 6: Ring Opening via Rearrangement 788
40.1.6 Product Subclass 6: Azetidines 802
40.1.6.1 Synthesis of Product Subclass 6 802
40.1.6.1.1 Ring-Closure Reactions 802
40.1.6.1.1.1 Method 1: Ring Closure of Amines and 1,3-Functionalized Hydrocarbons 802
40.1.6.1.1.1.1 Variation 1: From Amines and 1,3-Dihalo Compounds 802
40.1.6.1.1.1.2 Variation 2: From Amines and 1,3-Diol Derivatives 803
40.1.6.1.1.2 Method 2: Thermal [2 + 2] Cycloaddition of Imines and Alkenes 804
40.1.6.1.1.3 Method 3: Ring Closure of Acyclic Amines 805
40.1.6.1.1.3.1 Variation 1: Of .-Haloamines 805
40.1.6.1.1.3.2 Variation 2: Of .-Amino Alcohols and Derivatives 806
40.1.6.1.1.3.3 Variation 3: Of Alkenyl- or Allenylamines 811
40.1.6.1.1.3.4 Variation 4: Of .,d-Epoxyamines 813
40.1.6.1.1.3.5 Variation 5: Of .-Azidoamines 814
40.1.6.1.1.4 Method 4: Ring Closure of Acyclic Imine Derivatives 814
40.1.6.1.1.5 Method 5: Ring Closure of Stabilized Carbanions (C--C Bond Formation). 817
40.1.6.1.1.5.1 Variation 1: Intramolecular Alkylation of ß-Amino Halides 818
40.1.6.1.1.5.2 Variation 2: Intramolecular Michael Addition 821
40.1.6.1.1.6 Method 6: Photochemical Cyclizations 822
40.1.6.1.1.6.1 Variation 1: Intermolecular Photochemical Cyclizations 822
40.1.6.1.1.6.2 Variation 2: Intramolecular Photochemical Cyclizations 823
40.1.6.1.1.7 Method 7: Cyclizations through Insertion of Carbenoids into N--H Bonds 825
40.1.6.1.1.8 Method 8: Cyclizations through Copper-Catalyzed Intramolecular N-Vinylation 827
40.1.6.1.1.9 Method 9: Cyclization of Amines with Alkenes via Azazircona-cyclopentanes 828
40.1.6.1.2 Reduction of Four-Membered Ring Compounds 829
40.1.6.1.2.1 Method 1: Reduction of Azetidin-2-ones (ß-Lactams) 829
40.1.6.1.2.2 Method 2: Alkenation of Azetidin-2-ones (ß-Lactams) 833
40.1.6.1.2.3 Method 3: Reduction of Azetidinium Ions 835
40.1.6.1.3 Ring-Transformation Reactions 836
40.1.6.1.3.1 Method 1: Ring Expansion of Three-Membered Rings 836
40.1.6.1.3.2 Method 2: Ring Contraction of Five- or Six-Membered Rings 839
40.1.6.1.3.3 Method 3: Ring Transformation of 3-(Chloromethyl)azetidin-2-ones 841
40.1.7 Product Subclass 7: Ammonium Compounds and Nitrogen Ylides 846
40.1.7.1 Synthesis of Product Subclass 7 846
40.1.7.1.1 Method 1: Synthesis of Quaternary Ammonium Compounds from Primary and Secondary Amines 846
40.1.7.1.2 Method 2: Synthesis from Amines and Diazomethane 847
40.1.7.1.2.1 Variation 1: From Amines and Activated Diazomethane 847
40.1.7.1.2.2 Variation 2: From Amino Acids 848
40.1.7.1.3 Method 3: Alkylation of Tertiary Amines 849
40.1.7.1.3.1 Variation 1: With Haloalkanes under Pressure 850
40.1.7.1.3.2 Variation 2: With Tertiary Oxonium Salts 850
40.1.7.1.3.3 Variation 3: With Dialkoxycarbenium Salts 851
40.1.7.1.3.4 Variation 4: With Methyl Trifluoromethanesulfonate 852
40.1.7.1.3.5 Variation 5: With Methyl Chloroformate 853
40.1.7.1.3.6 Variation 6: With O-Alkylisoureas 854
40.1.7.1.3.7 Variation 7: With Dimethyl Sulfate 855
40.1.7.1.3.8 Variation 8: With Electron-Poor Alkenes and Alkynes 856
40.1.7.1.3.9 Variation 9: With Alkylideneammonium Halides 858
40.1.7.1.3.10 Variation 10: Synthesis of Polymer-Bound Ammonium Compounds 859
40.1.7.1.4 Method 4: Synthesis of Compounds Containing Several Quaternary Ammonium Centers 859
40.1.7.1.4.1 Variation 1: Derivatives of Diamines 859
40.1.7.1.4.2 Variation 2: Derivatives of Bis(aminomethyl)arenes 861
40.1.7.1.4.3 Variation 3: Derivatives of N-Alkylated Macrocycles 863
40.1.7.1.5 Method 5: Synthesis of Nitrogen Ylides 864
40.1.7.1.5.1 Variation 1: From Quaternary Ammonium Compounds 864
40.1.7.1.5.2 Variation 2: Addition of a Tertiary Amine to a Metal Carbene 865
40.1.7.1.5.3 Variation 3: Addition of a Tertiary Amine to the Simmons--Smith Reagent 866
40.1.7.2 Applications of Product Subclass 7 in Organic Synthesis 867
Keyword Index 874
Author Index 932
Abbreviations 978