Comprehensive Organic Synthesis, 9 volume set

Contents of All Volumes......Page 1
Front Matter......Page 8
Preface......Page 10
Contributors to Volume 8......Page 12
Table of Contents......Page 15
1.1.1 Introduction......Page 18
1.1.1.1 Kinetics and Mechanism......Page 19
1.1.2.1 Acyclic Carbonyl Compounds......Page 20
1.1.2.2 Cyclic Carbonyl Compounds......Page 22
1.1.3.1 Acyclic Carbonyl Compounds......Page 24
1.1.3.2 Cyclic Carbonyl Compounds......Page 31
1.1.4.1 Reduction of Enones......Page 32
1.1.4.2 Aldehydes versus Ketones......Page 33
1.1.4.3 Ketones versus Other Carbonyl Groups......Page 35
1.1.4.5 alpha-Halo Ketones......Page 36
1.1.5.1 Silicon......Page 37
1.1.5.2 Tin......Page 38
1.1.6 References......Page 39
1.2.1 Introduction......Page 42
1.2.2.1 General Considerations and Comparisons to Carbonyl Reductions......Page 43
1.2.2.2 Reduction of Preformed Imines and Iminium Salts of Ammonia, Primary and Secondary Amines......Page 44
1.2.2.3 Reduction of In Situ Generated Imines and Iminium Salts of Ammonia, Primary and Secondary Amines; Reductive Amination......Page 64
1.2.2.4 Reduction of Enamines via Iminium Ion Intermediates......Page 72
1.2.3.1 Reduction of Oximes, Oxime Ethers and Oxime Esters to Hydroxylamines and Derivatives......Page 77
1.2.3.3 Stereoselectivity of Reductions of Cyclic Oximes and Oxime Derivatives......Page 81
1.2.3.4 Reduction of Hydrazone Derivatives to Hydrazine Derivatives......Page 87
1.2.4 References......Page 91
1.3.1 Introduction......Page 96
1.3.2.1 Structural Types That May Donate Hydride......Page 97
1.3.2.2 Some Mechanisms for Hydride Donation......Page 98
1.3.2.3 Catalysis......Page 99
1.3.3.1 Hydride Transfer from Formic Acid......Page 101
1.3.3.2 Hydride Transfer from Aldehydes......Page 103
1.3.3.3 Hydride Transfer from Alcohols and Amines......Page 105
1.3.3.4 Hydride Transfer from Hydrocarbons......Page 108
1.3.3.5 Hydride Transfer from Heterocycles......Page 109
1.3.3.6 Hydride Transfer from Organometallics......Page 115
1.3.4 References......Page 120
1.4.1 Introduction......Page 124
1.4.2.1 Early Mechanistic Studies......Page 125
1.4.2.2 Reduction in the Absence of Proton Donors......Page 126
1.4.2.3 Reduction in the Presence of Proton Donors......Page 127
1.4.3.1 Reaction Medium......Page 128
1.4.3.3 Chemoselectivity......Page 130
1.4.3.4 Stereoselectivity......Page 133
1.4.4.1 Reduction of Imines and Oximes......Page 140
1.4.5 References......Page 143
1.5.1 Introduction......Page 145
1.5.2.1 Nonalkenic Ketones and Aldehydes......Page 147
1.5.2.2 Alkenic and Alkynic Ketones and Aldehydes......Page 150
1.5.3.1 Electroreduction of Acyclic and Cyclic Compounds with a C=N Bond......Page 151
1.5.4 References......Page 153
1.6.1 Introduction......Page 155
1.6.2.1 Hydrogenation of Aldehydes......Page 156
1.6.2.2 Hydrogenation of Ketones......Page 157
1.6.3.2 Hydrogenation of Schiff\'s Bases Aldimines and Ketimines......Page 159
1.6.4.1 Asymmetric Hydrogenation of the C=O Bond......Page 160
1.6.4.2 Asymmetric Hydrogenation of the C=N Bond......Page 161
1.6.5.1 Hydrogenation Using a Chirally Modified Catalyst......Page 165
1.6.6.1 Homogeneous Hydrogenation by Rhodium or Other Complexes......Page 168
1.6.7 References......Page 171
1.7.2 Asymmetric Reductions of the Carbonyl Group......Page 175
1.7.2.1 Chirally Modified Lithium Aluminum Hydride Reagents......Page 176
1.7.2.3 Asymmetric Reduction with Chirally Modified Boranes and Alanes......Page 186
1.7.2.4 Asymmetric Hydrosilylation......Page 189
1.7.2.5 Asymmetric Reduction of the C=N Double Bond......Page 192
1.7.4 References......Page 196
1.8.1 Introduction......Page 199
1.8.3 Sources of Enzymes and Microorganisms......Page 200
1.8.6.1 Enantiomeric Distinctions......Page 201
1.8.6.2 Enantiotopic Face Distinctions......Page 203
1.8.6.3 Diastereotopic Face Distinctions......Page 208
1.8.6.4 Combinations of Specificity......Page 209
1.8.6.5 Preparations of Deuterated or Tritiated Alcohols......Page 219
1.8.7 Reduction of C=N to CHNH......Page 220
1.8.9 Future Developments......Page 221
1.8.10 References......Page 223
1.9.1 Introduction......Page 226
1.9.2.2 Reduction with Dissolving Metals......Page 227
1.9.2.3 Reduction with Metal Hydrides......Page 228
1.9.3 Selective Reductions......Page 231
1.9.3.1 Acyclic Ketals......Page 232
1.9.3.2 Furanosides and Pyranosides......Page 233
1.9.3.3 Spiroketals......Page 235
1.9.3.4 Dioxolanes and Dioxanes......Page 236
1.9.3.5 Bicyclic Acetals and Ketals......Page 242
1.9.3.6 Azaacetals and Azaketals......Page 243
1.9.3.7 Thioacetals and Thioketals......Page 244
1.9.4 References......Page 247
1.10 Reduction of Carboxylic Acid Derivatives to Alcohols, Ethers and Amines......Page 250
1.10.1.2 Electrochemical and Dissolving Metal Reductions......Page 251
1.10.1.3 Reductions Using Metal Hydride Reagents......Page 252
1.10.2.1 Hydrogenation Reactions......Page 254
1.10.2.3 Reductions Using Metal Hydride Reagents......Page 255
1.10.3.2 Electrochemical and Dissolving Metal Reductions......Page 257
1.10.3.3 Reductions Using Metal Hydride Reagents......Page 259
1.10.4.1 Hydrogenation Reactions......Page 261
1.10.4.3 Reductions Using Metal Hydride Reagents......Page 262
1.10.5.2 Electrochemical and Dissolving Metal Reductions......Page 263
1.10.5.3 Reductions Using Metal Hydride Reagents......Page 264
1.10.6.1 Hydrogenation Reactions......Page 266
1.10.6.2 Electrochemical and Dissolving Metal Reductions......Page 267
1.10.6.3 Reductions Using Metal Hydride Reagents......Page 268
1.10.8 References......Page 269
1.11.1 Introduction......Page 273
1.11.2 Carboxylic Acids......Page 274
1.11.3 Acyl Halides......Page 276
1.11.4 Esters of Carboxylic Acids Including Ortho Esters......Page 280
1.11.5 Lactones......Page 282
1.11.6 Amides of Carboxylic Acids......Page 283
1.11.7 Lactams and Cyclic Imides......Page 287
1.11.8 Nitriles......Page 288
1.11.9 Miscellaneous Reductions to Aldehydes......Page 289
1.11.10 Reviews and Books......Page 292
1.11.11 References......Page 293
1.12.1 Introduction......Page 296
1.12.2 Carboxylic Acids......Page 297
1.12.3 Acyl Chlorides......Page 299
1.12.4 Carboxylic Acid Anhydrides......Page 304
1.12.5 Carboxylic Acid Esters......Page 305
1.12.7 Carboxylic Acid Amides......Page 306
1.12.8 Nitriles......Page 311
1.12.9 Imidoyl Chlorides......Page 313
1.12.10 Amidines, Imidates and Thioimidates......Page 315
1.12.11 Thioamides, Thioesters and Dithioesters......Page 316
1.12.12 References......Page 317
1.13.1 Introduction......Page 319
1.13.2.1 Reduction with Alkali Metals in Liquid Ammonia......Page 320
1.13.2.2 Clemmensen Reduction......Page 321
1.13.3.1 Reduction with NaBH_4 , LiAIH_4 and Related Reagents......Page 325
1.13.3.2 Reduction with BH_3 , DIBAL-H and Related Reagents......Page 327
1.13.3.3 Ionic Hydrogenation......Page 329
1.13.4.1 Catalytic Hydrogenation......Page 331
1.13.4.2 Hydrogen Transfer Reduction......Page 332
1.13.6 Miscellaneous......Page 333
1.13.7 References......Page 336
1.14 Reduction of C=X to CH_2 by Wolff-Kishner and Other Hydrazone Methods......Page 338
1.14.2.1 General Procedures and Mechanistic Aspects......Page 339
1.14.2.2 Modified Procedures......Page 340
1.14.2.3 Scope and Limitations......Page 349
1.14.3 Reduction of Aldehyde and Ketone Arylsulfonylhydrazones with Hydride Reagents......Page 354
1.14.3.2 Reductions with Sodium Borohydride......Page 356
1.14.3.3 Reductions with Sodium Cyanoborohydride......Page 361
1.14.3.4 Reductions with Catechol Borane and Related Reagents......Page 367
1.14.4 References......Page 370
2.1.1 Introduction......Page 374
2.1.3 Reduction of Aromatic Nitro and Nitroso Compounds to Azo and Azoxy Compounds......Page 375
2.1.4 Reduction of Aromatic Nitro and Nitroso Compounds to Hydroxylamines......Page 377
2.1.5.1 Transfer Hydrogenation......Page 378
2.1.5.2 Borohydride and Borane Reductions......Page 380
2.1.5.3 Reductions Involving Tellurium, Selenium and Sulfur......Page 381
2.1.5.4 Transition Metal Reductions......Page 382
2.1.5.6 Carbon Monoxide......Page 383
2.1.6 Reduction of Aliphatic Nitro Compounds to Hydroxylamines......Page 384
2.1.7.1 Nitroalkane Reductions......Page 385
2.1.7.2 Nitroalkene Reductions......Page 386
2.1.8 References......Page 388
2.2.1 Introduction......Page 391
2.2.2.1 Reduction to N-N Bonded Groups......Page 392
2.2.2.2 Reductive Cleavage......Page 393
2.2.3.1 Cleavage of Hydrazones......Page 397
2.2.3.2 Cleavage of Hydrazines, Hydrazides and N-Nitrosamines......Page 398
2.2.4.2 Deoxygenation of Nitrones, Nitrile Oxides and Tertiary Amine Oxides......Page 400
2.2.4.3 Reduction of Oximes to Imines......Page 402
2.2.4.4 Reduction of Hydroxylamines to Amines......Page 404
2.2.5.3 Reduction of Disubstituted Peroxides......Page 406
2.2.5.4 Reductive Ozonolysis of Alkenes......Page 408
2.2.6 References......Page 409
2.3.1 Introduction......Page 413
2.3.2.1 Reduction Deoxygenation of Sulfoxides......Page 414
23.2.2 Reduction of Sulfones......Page 417
2.3.2.3 Reduction of Sulfonic and Sulfinic Acids and Their Derivatives......Page 418
2.3.2.4 Reduction of Sulfimides Sulfilimines and Sulfoximides Sulfoximines......Page 419
2.3.2.5 Reduction of Se and Te Analogs......Page 420
2.3.3 Reduction of P=O Compounds......Page 421
2.3.4.1 Reduction of Disulfides and Diselenides......Page 422
2.3.5 References......Page 423
3.1 Heterogeneous Catalytic Hydrogenation of C=C and C tbond C......Page 426
3.1.1.2 Catalysts......Page 427
3.1.2.2 Kinetics......Page 428
3.1.2.3 Mechanism......Page 429
3.1.3 Hydrogenation of C=C......Page 430
3.1.3.1 Double Bond Migration......Page 431
3.1.3.2 Structure - Reactivity......Page 433
3.1.3.3 Stereochemistry......Page 435
3.1.3.4 Haptophilicity......Page 438
3.1.4.1 Semihydrogenation......Page 439
3.1.4.2 Mechanism......Page 440
3.1.4.3 Regio- and Stereo-Selectivity......Page 441
3.1.5.3 Conjugated Diene Mechanisms......Page 442
3.1.5.4 Allenes and Cumulenes......Page 443
3.1.6.1 Structure - Reactivity......Page 445
3.1.6.3 Stereochemistry......Page 446
3.1.7.1 Regioselectivity......Page 447
3.1.8.2 Conjugated Functional Groups......Page 448
3.1.10 References......Page 449
3.2.1 Hydrogenation of Nonconjugated C=C Bonds......Page 452
3.2.2.2 Dienes and Trienes to Alkenes by 1,2-Reduction......Page 458
3.2.2.3 Dienes to Alkenes by 1,4-Reduction......Page 460
3.2.2.4 Hydrogenation of C=C Bonds Conjugated with Aromatic Rings, CN, CO, CO_2 R, etc.......Page 461
3.2.3 Hydrogenation of Aromatic and Heteroaromatic Rings......Page 462
3.2.4.1 Reduction of C tbond C Bonds to Saturated Hydrocarbons......Page 465
3.2.4.3 Reduction of C tbond C Bonds to cis-Alkenes......Page 466
3.2.4.4 Reduction of C tbond C Bonds to trans-Alkenes......Page 467
3.2.5.1 Chiral Catalysts......Page 468
3.2.5.2 Asymmetric Hydrogenation of Enamides and Related Substrates......Page 469
3.2.5.3 Asymmetric Hydrogenation of Acrylic Acids and Esters......Page 470
3.2.5.4 Asymmetric Hydrogenation of Allylic Alcohols......Page 471
3.2.6 References......Page 472
3.3.1 Introduction......Page 479
3.3.2.3 Mechanism of Reduction by Diimide......Page 480
3.3.2.4 Scope and Limitations......Page 484
3.3.3.2 Mechanisms of Dissolving Metal Reductions......Page 486
3.3.3.3 Scope and Limitations......Page 487
3.3.4.1 Introduction......Page 489
3.3.4.2 Mechanism of the Reduction of C=C and C tbond C by Cr^II......Page 490
3.3.5.2 Mechanism of Metal Hydride - Transition Metal Halide Reductions......Page 491
3.3.5.3 Scope and Limitations......Page 493
3.3.6.2 Mechanism of the Ionic Hydrogenation Reaction......Page 494
3.3.7 References......Page 495
3.4 Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods......Page 497
3.4.2 The Birch Reduction......Page 498
3.4.2.1 Experimental Procedures......Page 500
3.4.3.1 Benzenoid Hydrocarbons and Ethers......Page 501
3.4.3.3 Biphenyls, Fluorenes and Fused Polycyclic Hydrocarbons......Page 504
3.4.3.4 Phenols......Page 505
3.4.3.5 Aromatic Amines......Page 506
3.4.3.6 Carboxylic Acids......Page 507
3.4.3.7 Aromatic Carboxylic Esters......Page 513
3.4.3.8 Aromatic Amides......Page 515
3.4.3.9 Aromatic Ketones......Page 516
3.4.3.10 Aryl- and Benzyl-Silanes......Page 521
3.4.3.11 Hydrogenolysis during Birch Reductions......Page 522
3.4.4.1 The Benkeser Reduction......Page 524
3.4.4.4 Reductive Silylations......Page 525
3.4.4.5 Organometallic Procedures......Page 526
3.4.5 References......Page 527
3.5 Partial Reduction of Enones, Styrenes and Related Systems......Page 530
3.5.2.1 Dissolving Metal Reduction......Page 531
3.5.2.2 Reduction with Low-Valent Transition Metals......Page 538
3.5.2.3 Electrochemical Reduction......Page 539
3.5.3 Catalytic Hydrogenation......Page 540
3.5.4.1 Boron Hydrides......Page 543
3.5.4.2 Aluminum Hydrides......Page 548
3.5.4.3 Silicon Hydrides......Page 553
3.5.4.4 Tin Hydrides......Page 554
3.5.5.1 Copper Hydrides......Page 555
3.5.5.2 Iron Hydrides......Page 557
3.5.6.1 Transfer Hydrogenation Using Alcohols as Hydrogen Donors......Page 558
3.5.6.2 Transition Metal Catalyzed Reductions with Group 14 Metal Hydrides......Page 560
3.5.6.3 Transition Metal Catalyzed Reductions with Other Hydrogen Donors......Page 564
3.5.7.1 Enzymatic Reductions......Page 565
3.5.7.2 Biomimetic Reductions with NADPH Models......Page 568
3.5.8 Miscellaneous Reducing Agents......Page 570
3.5.9.1 Dissolving Metal Reduction......Page 571
3.5.9.2 Catalytic Hydrogenation......Page 572
3.5.9.3 Miscellaneous Reducing Agents......Page 575
3.5.10 References......Page 576
3.6.2.1 Metal Hydride Reductions......Page 586
3.6.2.3 Reduction with Sodium Dithionite......Page 596
3.6.2.4 Reduction with Formic Acid......Page 597
3.6.2.5 One-Electron Reduction......Page 598
3.6.3 Hydrogenation......Page 604
3.6.4 References......Page 607
3.7 Partial and Complete Reduction of Pyrroles, Furans, Thiophenes and Their Benzo Analogs......Page 610
3.7.2.1 Catalytic Hydrogenation......Page 611
3.7.2.2 Dissolving Metals and Metals in Acid......Page 612
3.7.3.1 Catalytic Hydrogenation......Page 613
3.7.3.2 Dissolving Metals......Page 614
3.7.4.1 Catalytic Hydrogenation......Page 615
3.7.4.2 Dissolving Metals......Page 616
3.7.4.3 Ionic Hydrogenation......Page 617
3.7.4.5 Miscellaneous Methods......Page 618
3.7.5.1 Catalytic Hydrogenation......Page 619
3.7.5.2 Dissolving Metals and Metals in Acid......Page 621
3.7.5.3 Boron Hydrides and Related Methods......Page 623
3.7.6 Reduction of Benzo[b]Furans......Page 631
3.7.6.1 Catalytic Hydrogenation......Page 632
3.7.6.2 Dissolving Metals......Page 633
3.7.6.3 Boron Hydrides and Related Methods......Page 634
3.7.6.4 Miscellaneous Methods......Page 635
3.7.7.2 Dissolving Metals......Page 636
3.7.8 References......Page 637
3.8 Partial and Complete Reduction of Heterocycles Containing More Than One Heteroatom......Page 641
3.8.2.1 Five-Membered Ring Systems......Page 642
3.8.2.2 Six-Membered Ring Systems......Page 646
3.8.3.1 Five-Membered Ring Systems......Page 650
3.8.3.2 Six-Membered Ring Systems......Page 658
3.8.4.1 Five-Membered Ring Systems......Page 662
3.8.4.2 Six-Membered Ring Systems......Page 664
3.8.5.1 Dioxolanes, Dioxanes, Dithioles and Benzodithioles......Page 665
3.8.6.1 Triazoles, Triazolium Salts and Benzotriazoles......Page 667
3.8.7.1 Oxadiazoles and Benzoxadiazoles......Page 669
3.8.8 References......Page 670
3.9.1 Introduction......Page 673
3.9.2 Mechanistic Aspects......Page 674
3.9.2.1 Thermodynamic Considerations......Page 675
3.9.2.2 Detailed Mechanism of Hydrometallation......Page 677
3.9.3.1 Synthesis, Structure and Properties of Reagents......Page 681
3.9.3.2 Hydrozirconation of Alkenes and Alkynes......Page 682
3.9.3.3 Selectivity Issues......Page 689
3.9.3.4 Synthetic Utilization of Hydrozirconation......Page 696
3.9.4.1 Hydrometallation with Other Transition Metals......Page 701
3.9.4.2 Catalytic Hydrometallation with Main Group Metals......Page 703
3.9.5 References......Page 705
3.10.1.1 Introduction......Page 709
3.10.1.2 Fundamentals of the Hydroboration Reaction......Page 710
3.10.2.1 Hydroboration with Boran - Tetrahydrofuran......Page 711
3.10.2.2 Hydroboration with Other Sources of Borane......Page 714
3.10.3.1 Hydroboration with Thexylborane and Other Alkyl- and Aryl-Boranes......Page 715
3.10.3.2 Hydroboration with Monohaloboranes......Page 716
3.10.4.1 General Considerations......Page 718
3.10.4.2 Hydroboration with 9-BBN-H......Page 719
3.10.4.3 Hydroboration with Other Dialkyl- and Diaryl-Boranes......Page 721
3.10.4.4 Hydroboration with Dihaloboranes......Page 724
3.10.4.6 Hydroboration with Catecholborane and Related Compounds......Page 725
3.10.5.1 General Considerations......Page 726
3.10.5.2 Survey of Reactions......Page 727
3.10.7.1 General Considerations......Page 730
3.10.7.2 Protonolysis of Alkylboranes with Carboxylic Acids: Synthesis of Alkanes......Page 731
3.10.7.3 Protonolysis of Alkenylboranes: Synthesis of Alkenes and Dienes......Page 732
3.10.8 References......Page 733
3.11 Hydroalumination of C=C and C tbond C......Page 738
3.11.1.2 Historical Context and Development......Page 739
3.11.1.3 Sources of the Aluminum Hydrides......Page 741
3.11.1.5 Potential of Resulting Organoaluminum Reagents in Organic Synthesis......Page 742
3.11.2.1 Suitable Alkenic Substrates......Page 744
3.11.2.2 Suitable Alkynic Substrates......Page 745
3.11.2.4 Interfering Functional Groups......Page 747
3.11.2.6 Selectivity......Page 749
3.11.2.7 Modifications in the Hydroalumination Process......Page 751
3.11.3.1 Reaction Rates and Kinetic Rate Expressions......Page 752
3.11.3.2 Substituent Effects on Relative Rates of Alkynes......Page 754
3.11.3.4 Stereochemical Effects of Lewis Acids and Bases......Page 755
3.11.3.5 Kinetic Effects of Transition Metals......Page 756
3.11.4.1 Experimental Conditions: Protolysis and Oxidation......Page 758
3.11.4.3 Metallodealumination......Page 759
3.11.4.4 Carbodealumination......Page 760
3.11.4.5 Carbalurnination......Page 761
3.11.5.1 Dienes, Polyenes and Enynes......Page 762
3.11.5.3 Carbocyclizations......Page 763
3.11.6 References......Page 764
3.12.1 Introduction......Page 767
3.12.1.1 Catalysts......Page 768
3.12.1.4 Mechanism......Page 769
3.12.2.1 Hydrosilylation of Acetylene......Page 773
3.12.2.2 Hydrosilylation of Monosubstituted Alkynes......Page 774
3.12.2.3 Hydrosilylation of Disubstituted Alkynes......Page 775
3.12.3 Hydrosilylation of Conjugated Carbon-Carbon Triple Bonds......Page 776
3.12.4.1 Hydrosilylation of Ethylene......Page 777
3.12.4.2 Hydrosilylation of Monosubstituted Alkenes......Page 778
3.12.4.3 Hydrosilylation of Disubstituted and More Highly Substituted Alkenes......Page 780
3.12.5.1 Hydrosilylation of Acyclic Polyenes......Page 782
3.12.5.2 Hydrosilylation of Cyclic Polyenes......Page 784
3.12.6 Hydrosilylation of Conjugated Enones......Page 785
3.12.7 Asymmetric Hydrosilylation of Carbon-Carbon Double Bonds......Page 786
3.12.8.1 Reaction of Vinylsilanes with Electrophiles......Page 789
3.12.8.4 Aldol Reactions......Page 790
3.12.8.5 Synthetic Reactions of Pentafluorosilicates......Page 791
3.12.8.7 Hydrosilylation in the Presence of CO......Page 792
3.12.9 References......Page 793
4.1.1 Introduction and Scope of the Review......Page 797
4.1.3 Catalytic Hydrogenolysis......Page 798
4.1.4.1 Reductions with Metals Dissolving Metal Method......Page 799
4.1.4.2 Reduction with Low-Valent Metal Salts......Page 800
4.1.5.1 Tributyltin Hydride......Page 802
4.1.5.3 Other Metal Hydride Reagents......Page 805
4.1.6.1 Reduction with LiAlH_4......Page 806
4.1.6.3 Sodium Borohydride......Page 807
4.1.6.4 Lithium Triethylborohydride......Page 808
4.1.7 Miscellaneous Reduction Procedures......Page 810
4.1.8 References......Page 811
4.2.1 Introduction......Page 814
4.2.2.1 Hydride Reduction Methods......Page 815
4.2.2.2 Catalytic Hydrogenolysis......Page 817
4.2.2.3 Electron Transfer Reductions......Page 818
4.2.2.4 Stannane Reduction of O-Thiocarbonyl Derivatives......Page 821
4.2.2.5 Stannane and Silane Reduction of Esters and Carbonates......Page 827
4.2.3.1 Hydride and Hydrogenolysis Methods......Page 829
4.2.3.2 Deamination via Diazenes and Related Species......Page 831
4.2.3.3 Reduction of Isonitriles and Related Compounds......Page 833
4.2.4 References......Page 835
4.3.1.1 Introduction......Page 837
4.3.1.2 Raney Nickel and Nickel0 Complexes......Page 838
4.3.1.3 Hydrides or Organometallics Combined with Transition Metal Salts or Their Complexes......Page 841
4.3.1.4 Metals and Amalgams......Page 844
4.3.1.5 Tin Hydrides......Page 847
4.3.2.2 Raney Nickel......Page 849
4.3.2.4 Alkali Metals......Page 850
4.3.2.6 Miscellaneous Deselenations......Page 851
4.3.3.1 Protonolysis......Page 852
4.3.3.2 Metal Hydride Demercuration......Page 853
4.3.3.3 Miscellaneous Methods......Page 859
4.3.4.1 Reduction of Tervalent Organophosphorus Compounds......Page 860
4.3.4.2 Reduction of Tetravalent Organophosphorus Compounds......Page 862
4.3.4.3 Reduction of Pentavalent Organophosphorus Compounds......Page 865
4.3.5 References......Page 867
4.4.2 Reduction of Epoxides to Alcohols......Page 873
4.4.2.1 Metal Hydrides......Page 874
4.4.2.2 Dissolving Metals......Page 882
4.4.2.3 Hydrogenolysis......Page 883
4.4.2.4 Miscellaneous......Page 885
4.4.3 Deoxygenation of Epoxides......Page 886
4.4.3.1 Phosphorus Reagents......Page 887
4.4.3.2 Silicon and Tin Reagents......Page 888
4.4.3.3 Selenium and Tellurium Reagents......Page 889
4.4.3.4 Low-Valent Metals......Page 890
4.4.3.6 Miscellaneous......Page 892
4.4.4 References......Page 893
4.5.1 Hydrogenolysis of the Carbon-Halogen Bond in Vinyl Halides......Page 896
4.5.1.1 Hydrogenolysis of Vinylic Fluorides......Page 897
4.5.1.2 Hydrogenolysis of Vinylic Chlorides......Page 898
4.5.1.3 Hydrogenolysis of Vinylic Bromides......Page 900
4.5.1.4 Hydrogenolysis of Vinylic Iodides......Page 901
4.5.2.1 General......Page 902
4.5.2.2 Hydrogenolysis of Aryl Fluorides......Page 904
4.5.2.3 Hydrogenolysis of Aryl Chlorides......Page 905
4.5.2.4 Hydrogenolysis of Aryl Bromides......Page 907
4.5.2.5 Hydrogenolysis of Aryl Iodides......Page 909
4.5.3.2 Hydrogenolysis of Phenols and Their Derivatives......Page 911
4.5.4 Hydrogenolysis of Trigonal Carbon-Sulfur Bonds......Page 914
4.5.5.1 Hydrogenolysis of Enamines......Page 916
4.5.5.3 Hydrogenolysis of Arenediazonium Salts......Page 917
4.5.6 References......Page 922
4.6.1 Introduction......Page 924
4.6.3 Reduction and Subsequent Dehydration......Page 925
4.6.4 Reductive Elimination of alpha-Substituted Ketones......Page 926
4.6.5.1 Vinyl Esters......Page 931
4.6.5.2 Vinyl Ethers......Page 935
4.6.5.3 Vinyl Halides......Page 938
4.6.5.4 Enamines......Page 939
4.6.6 Reductive Elimination of Hydrazone Derivatives......Page 940
4.6.6.1 Formation of Arenesulfonylhydrazones......Page 941
4.6.6.2 The Aprotic Bamford-Stevens Reaction......Page 942
4.6.6.3 The Protic Bamford-Stevens Reaction......Page 944
4.6.6.4 The Shapiro Reaction......Page 945
4.6.7.1 Quinones to Arenes......Page 950
4.6.7.2 Ketones and 1,2-Diketones to Alkynes......Page 951
4.6.8 References......Page 952
4.7.1 Introduction......Page 955
4.7.2.1 Hydrogenolysis over Palladium with Molecular Hydrogen......Page 956
4.7.2.2 Hydrogenolysis over Palladium with Other Hydride Sources......Page 958
4.7.2.4 Hydrogenolysis over Raney Nickel......Page 963
4.7.3.1 Lithium Aluminum Hydride......Page 965
4.7.3.3 Sodium Borohydride......Page 967
4.7.3.5 Other Hydride Reducing Agents......Page 969
4.7.4.1 Lithium and Sodium in Liquid Ammonia......Page 971
4.7.4.2 Other Metals......Page 972
4.7.5 Electrolytic Reduction Processes......Page 974
4.7.6 Biomimetic Reducing Agents......Page 977
4.7.8 Miscellaneous Reducing Agents......Page 978
4.7.9 References......Page 979
4.8 Reduction of alpha-Substituted Carbonyl Compounds-CX-CO-to Carbonyl Compounds-CH-CO-......Page 982
4.8.1.2 Mechanisms of Bond Cleavage......Page 983
4.8.2.1 Reduction by Electron Transfer......Page 984
4.8.2.2 Reduction by Strong Nucleophiles......Page 987
4.8.3.1 Reduction by Electron Transfer......Page 990
4.8.4.1 Reduction by Electron Transfer......Page 992
4.8.6 The Carbon-Carbon Bond......Page 994
4.8.8 References......Page 995
Abbreviations......Page 997
A......Page 1000
B......Page 1003
C......Page 1009
D......Page 1013
E......Page 1016
F......Page 1017
G......Page 1020
H......Page 1024
I......Page 1029
J......Page 1030
K......Page 1032
L......Page 1037
M......Page 1040
N......Page 1047
O......Page 1050
P......Page 1052
R......Page 1055
S......Page 1059
T......Page 1067
V......Page 1071
W......Page 1073
Y......Page 1076
Z......Page 1078
A......Page 1079
B......Page 1086
C......Page 1092
D......Page 1099
E......Page 1102
F......Page 1104
G......Page 1105
H......Page 1106
I......Page 1109
K......Page 1112
L......Page 1114
M......Page 1116
N......Page 1117
O......Page 1119
P......Page 1121
Q......Page 1127
R......Page 1128
S......Page 1130
T......Page 1134
V......Page 1137
Z......Page 1138