Comprehensive Organic Synthesis. Oxidation

Front Matter......Page 1
Z......Page 0
Table of Contents......Page 3
Preface......Page 6
Contributors to Volume 7......Page 8
Abbreviations......Page 11
1.1.1 Introduction......Page 14
1.1.4 Formation of R-M Bonds (M = Group I and II Metal)......Page 15
1.1.6 Formation of R-M Bonds (M = Transition Metal)......Page 16
1.1.7 Formation of R-C Bonds......Page 17
1.1.7.2 Alkane Dehydrodimerization......Page 18
1.1.7.4 Dehydrogenation and Aromatization......Page 19
1.1.7.6 Other Reactions......Page 20
1.1.9 Formation of R-N Bonds......Page 21
1.1.11.1 Autoxidation......Page 23
1.1.11.2 Hydroxylation and Related Reactions......Page 24
1.1.12 Formation of R-X Bonds (X = S, Se, Te)......Page 27
1.1.14 Formation of R-X Bonds (X = C1, Br, I)......Page 28
1.1.15 References......Page 30
1.2.1 Introduction......Page 34
1.2.2.2 Reactivity......Page 35
1.2.3.1 Intermolecular......Page 36
1.2.3.2 Intramolecular......Page 40
1.2.4 Intramolecular Insertion into sp^2 C-H Bonds......Page 44
1.2.5 References......Page 50
1.3.1.1 Topics Covered......Page 52
1.3.2 Intramolecular Functionalizations in the Vicinity of Existing Substrate Functional Groups......Page 53
1.3.3.1 Remote Photochemical Functionalization......Page 55
1.3.3.3 Directed Chlorinations......Page 56
1.3.4 Selective Reactions in Molecular Complexes......Page 62
1.3.5 Future Prospects for Remote Oxidations......Page 63
1.3.6 References......Page 64
1.4.1 Introduction......Page 66
1.4.2.3 Use of Microorganisms......Page 68
1.4.3.1 Acyclic Hydracarbons and Their Functionalized Derivatives......Page 69
1.4.3.2 Cyclic Hydrocorbons and Their Functionalized Derivatives......Page 71
1.4.3.3 Isoprenoids......Page 75
1.4.3.4 Alkaloids......Page 78
1.4.4 Microbial Oxidation of Steroids......Page 79
1.4.4.1 Dehydrogenation......Page 80
1.4.4.2 Hydroxylation......Page 81
1.4.5 Special Methods......Page 87
1.4.5.1 Benzylic Substrates......Page 88
1.4.5.2 Allylic Substrates......Page 90
1.4.5.3 Nuclear Hydroxylation of Aromatic Hydrocarbons......Page 91
1.4.6.1 Oxidations with Isolated Enzymes......Page 92
1.4.7 References......Page 93
2.1.1 Introduction......Page 96
2.1.2.1 Selenium Dioxide Based Reagents......Page 97
2.1.2.2 Metal Acetates and Related Reagents......Page 105
2.1.2.3 Miscellaneous Reagents......Page 108
2.1.3.1 Chromium(VI)-Based Reagents......Page 112
2.1.3.2 Other Transition Metal Catalyzed Allylic Oxidations......Page 120
2.1.3.3 Selenium-Based Reagents......Page 121
2.1.3.4 Singlet Oxygen......Page 123
2.1.3.5 Miscellaneous Reagents......Page 125
2.1.4 References......Page 126
2.2.1 Introduction......Page 131
2.2.2.1 Halogenation......Page 132
2.2.2.2 Dehydrohalogenation......Page 134
2.2.3 Sulfur-Based Reagents......Page 136
2.2.3.1 Sulfur(II) Reagents......Page 137
2.2.3.2 Sulfur(IV) Reagents......Page 139
2.2.4 Selenium-Based Reagents......Page 140
2.2.4.1 Selenium(II) Reagents......Page 141
2.2.4.2 Selenium(IV) Reagents......Page 144
2.2.5 Dichlorodicyanoquinone and Related Reagents......Page 147
2.2.6 Noble Metals and Their Salts......Page 151
2.2.7 Miscellaneous Chemical Methods......Page 154
2.2.8 Microbial and Enzymatic Methods......Page 157
2.3.10 References......Page 158
2.3.1 Introduction......Page 162
2.3.2.1 Saturated Ketones......Page 163
2.3.2.2 alpha,beta-Unsaturated Ketones: sp^3 Center......Page 185
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2.3.2.4 Esters and Lactones......Page 190
2.3.2.5 Amides and Lactams......Page 194
2.3.2.6 Carboxylic Acids......Page 196
2.3.3.1 Oxime Acetates and Nitrones......Page 197
2.3.4 References......Page 198
2.4.1 Introduction......Page 203
2.4.2 The Pummerer Rearrangement......Page 204
2.4.3.1 Reaction with Carboxylic Anhydrides......Page 206
2.4.3.2 Pummerer Rearrangement with alpha-Alkylation and Arylation......Page 209
2.4.3.3 Pummerer Rearrangement with Participation by Nitrogen......Page 211
2.4.3.4 Pummerer Rearrangement in Hydroxylic Solvents......Page 212
2.4.3.5 Miscellaneous and Abnormal Pummerer Rearrangements......Page 213
2.4.4 alpha-Halogenation of Sulfides......Page 216
2.4.4.1 Miscellaneous Routes to alpha-Chloro Sulfides......Page 222
2.4.5 References......Page 224
2.5 Oxidation Adjacent to Nitrogen......Page 227
2.5.2.1 The Nef Reaction......Page 228
2.5.2.2 The Meyer Reaction......Page 230
2.5.3.2 Chromium and Manganese Reagents......Page 231
2.5.3.5 Amine Oxides......Page 232
2.5.3.6 Miscellaneous Oxidation Reactions of Tertiary Amines......Page 233
2.5.4.2 N-Nitrosamines......Page 234
2.5.4.3 Amides......Page 235
2.5.4.4 Urethanes......Page 236
2.5.4.5 Miscellaneous Methods......Page 237
2.5.5.1 Conversion into Aldehydes and Ketones......Page 238
2.5.6.1 Alkylation......Page 239
2.5.7.1 Lactams/Amides......Page 240
2.5.7.4 Hydrazones/Oximes......Page 241
2.5.8 References......Page 242
2.6.1 Introduction......Page 245
2.6.2.1 Introduction......Page 246
2.6.2.2 Reaction Conditions......Page 247
2.6.2.3 Selectivity of Reaction and Application in Synthesis......Page 248
2.6.3.1 Introduction......Page 254
2.6.3.3 Selectivity of Reaction and Application in Synthesis......Page 255
2.6.4.3 Electrochemical Oxidation......Page 257
2.6.5 References......Page 258
2.7 Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents......Page 261
2.7.2.3 In DMF/DMSO with Catalytic Sulfuric Acid......Page 262
2.7.2.5 In Aqueous Sulfuric Acid/Acetone (Jones Oxidation)......Page 263
2.7.3.1 Chromium(VI) Oxide(Pyridine)_2......Page 266
2.7.3.3 Pyridinium Chlorochromate (PCC)......Page 270
2.7.3.4 Other Chromates......Page 277
2.7.3.5 Pyridinium Dichromate (PDC)......Page 282
2.7.3.6 Other Dichromates......Page 287
2.7.4.3 Catalytic Chromium(VI) Oxide Oxidations......Page 288
2.7.5.1 On Inert Inorganic Supports......Page 289
2.7.5.2 On Resins/Polymers......Page 290
2.7.5.3 On Carbon......Page 292
2.7.6.2 Trimethylsilyl Chlorochromate (TMSCC)......Page 293
2.7.6.3 Alkyl Metal Chromates......Page 295
2.7.7 References......Page 296
2.8.1 Introduction......Page 300
2.8.2 General Mechanism of Activated DMSO Oxidation......Page 301
2.8.3.1 DMSO - Dicyclohexylcarbodiimide......Page 302
2.8.3.2 DMSO - Acetic Anhydride......Page 303
2.8.3.3 DMSO - Trifluoroacetic Anhydride......Page 304
2.8.3.5 DMSO-Oxalyl Chloride......Page 305
2.8.3.7 DMSO - Chlorine and Halogen Derivatives......Page 307
2.8.4 Oxidation of Alcohols......Page 308
2.8.5 Conclusions......Page 311
2.8.6 References......Page 312
2.9.2.1 Selective Preparation of Aldehydes......Page 313
2.9.2.2 Selective Preparation of Lactones from Diols......Page 320
2.9.3.1 Selective Preparation of Ketones......Page 326
2.9.4 Conclusion......Page 332
2.9.5 References......Page 333
2.10.1 Introduction......Page 336
2.10.2.1 Imidazolones......Page 337
2.10.2.4 Estrogens......Page 338
2.10.2.5 Miscellaneous......Page 340
2.10.3.1 Indoles......Page 342
2.10.3.3 Dihydrocoumarins......Page 343
2.10.4.3 Quinol Acetates......Page 345
2.10.5 Nonmetallated Intermediates......Page 346
2.10.5.1 Hydroquinones......Page 347
2.10.5.3 Anthracycline Relatives......Page 348
2.10.6 References......Page 349
2.11.1 Introduction......Page 351
2.11.2.1 Towards Rubradirin......Page 352
2.11.2.4 Lavendamycin Pharmacophores......Page 353
2.11.2.5 Methoxatin......Page 355
2.11.3.3 Saframycin B......Page 356
2.11.3.4 Demethoxydaunomycinone......Page 357
2.11.4.1 Demethoxydaunomycinone......Page 358
2.11.4.2 Towards Mitomycin C......Page 359
2.11.5.1 Metacyclophanes......Page 360
2.11.5.3 Miscellaneous......Page 361
2.11.6 References......Page 362
3.1 Addition Reactions with Formation of Carbon-Oxygen Bonds: (i) General Methods of Epoxidation......Page 363
3.1.2.1 General Survey of Reactivity......Page 364
3.1.2.2 Epoxidations with m-Chloroperbenzoic Acid (MCPBA)......Page 365
3.1.2.3 Some of the Commonly Used Peroxy Acids and Related Reagents......Page 378
3.1.3.1 Epoxidations of Alkenes Lacking Directing Groups......Page 381
3.1.3.2 Epoxidations of Cyclic Alkenes Having Directing Groups......Page 382
3.1.3.3 Epoxidations of Acyclic Alkenes Having Directing Groups......Page 384
3.1.5 Epoxidations with Hydrogen Peroxide......Page 387
3.1.7 Epoxidations via Catalysis by First-Row Transition Metal Complexes......Page 388
3.1.9 Chemoselective Epoxidations......Page 390
3.1.10 References......Page 392
3.2 Addition Reactions with Formation of Carbon-Oxygen Bonds: (ii) Asymmetric Methods of Epoxidation......Page 394
3.2.2 Fundamental Elements of Titanium Tartrate Catalyzed Asymmetric Epoxidation......Page 395
3.2.3.1 Stoichiometry......Page 398
3.2.3.4 Oxidant and Epoxidation Solvent......Page 399
3.2.3.6 Titanium Alkoxides......Page 400
3.2.4 Sources of Allylic Alcohols......Page 401
3.2.5.1 Allyl Alcohol......Page 402
3.2.5.2 2-Substituted Allyl Alcohols......Page 403
3.3.5.3 (3E)-Substituted Allyl Alcohols......Page 405
3.2.5.4 (3Z)-Monosubstituted Allyl Alcohols......Page 410
3.2.5.5 (2,3E)-Disubstituted Allyl Alcohols......Page 411
3.2.5.6 (2,3Z)-Disubstituted Allyl Alcohols......Page 413
3.2.5.8 2,3,3-Trisubstituted Allyl Alcohols......Page 414
3.2.5.9 1-Substituted Allyl Alcohols: Kinetic Resolution......Page 416
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3.2.5.10 1,1-Disubstituted Allyl Alcohols......Page 422
3.2.5.11 Homoallylic, Bis(Homoallylic) and Tris(Homoallylic) Alcohols......Page 424
3.2.6 Mechanism of the Titanium Tartrate Catalyzed Asymmetric Epoxidation......Page 425
3.2.7.1 Ti_2 (Tartrate)_2 Complex......Page 427
3.2.7.2 Ti_2 (Tartrate) Complex......Page 428
3.2.7.4 [Ti(OPr^i )_2 Cl_2 (Tartrate)] Complexes......Page 429
3.2.8 Other Asymmetric Epoxidation Methods......Page 430
3.2.9 Homochiral Epoxides via Asymmetric Dihydroxylation......Page 434
3.2.10 References......Page 437
3.3.1 Introduction......Page 442
3.3.2.1 Osmium Tetroxide......Page 444
3.3.2.3 Methods Involving Halohydrin Esters as Intermediates......Page 449
3.3.3.2 Hydrogen Peroxide with an Oxide Catalyst......Page 451
3.3.4 References......Page 452
3.4.1 Introduction......Page 454
3.4.2.2 Solvents......Page 455
3.4.2.3 Reoxidants......Page 456
3.4.3.1 Oxidation of Terminal Alkenes Bearing Various Functional Groups......Page 457
3.4.3.2 Synthetic Applications......Page 459
3.4.4.2 Regioselective Oxidation of alpha,beta- and beta,gamma-Unsaturated Carbonyl Compounds......Page 467
3.4.4.3 Regioselective Oxidation of Allyl and Homoallyl Ethers and Esters......Page 470
3.4.5 References......Page 472
3.5 Addition Reactions with Formation of Carbon-Nitrogen Bonds......Page 474
3.5.2.1 Aziridines with Nitrogen Unsubstituted......Page 475
3.5.2.2 N-Alkyl- and N- Alkenyl-Aziridines......Page 479
3.5.2.3 N-Aryl- and N-Heteroaryl-Aziridines......Page 481
3.5.2.4 N-Acyl- and N-Cyano-Aziridines and Related Compounds......Page 482
3.5.2.5 N- Amiwaziridines, N-Phosphonylaziridines......Page 485
3.5.2.6 Aziridines N-Substituted with O or S......Page 488
3.5.3.1 Formation of Diamines......Page 489
3.5.3.2 Formation of Diazides......Page 492
3.5.4.1 Oxyamination and Oxyamidation......Page 493
3.5.5.1 Addition of Nitrogen and Sulfur......Page 498
3.5.5.2 Addition of Nitrogen and Selenium......Page 500
3.5.5.3 Addition of Nitrogen and Tellurium......Page 502
3.5.6.2 Addition of Nitrogen and Chlorine......Page 503
3.5.6.3 Addition of Nitrogen and Bromine......Page 505
3.5.6.4 Addition of Nitrogen and Iodine......Page 506
3.5.6.5 Iodolactamizations and Related Reactions......Page 508
3.5.7.1 Addition to Dienes......Page 509
3.5.10 Additions Cleaving the C=C Bond......Page 511
3.5.11 References......Page 513
3.6.2.1 Formation of Thiiranes......Page 519
3.6.2.2 Electrophilic Sulfur Additions......Page 520
3.6.2.3 Radical Sulfur Additions......Page 522
3.6.3.1 Regiochemistry of Additions......Page 524
3.6.3.2 Seleno-Heteroatom Additions......Page 526
3.6.3.3 Selenium-Induced Cyclizations......Page 527
3.6.4 References......Page 529
3.7.1 Oxidative Halogenation with Halometallic Reagents......Page 531
3.7.2 Halofunctionalizations with Hg^II , TI^III and Te^IV Reagents......Page 537
3.7.3 Oxidative Halogenation with Nonmetallic Reagents......Page 539
3.7.4 Miscellaneous (Photochemical and Enzymatic Reactions)......Page 542
3.7.5 References......Page 543
3.8.1 Introduction......Page 545
3.8.2.1 Ozone......Page 547
3.8.3.1 Ozone......Page 548
3.8.3.2 Permanganate......Page 562
3.8.3.4 Ruthenium Tetroxide......Page 568
3.8.3.5 Hexavalent Chromium Compounds......Page 575
3.8.4.1 Ozone Followed by an Oxidative Work-up......Page 578
3.8.4.2 Permanganate Reactions......Page 582
3.8.4.5 t-Butyl Peroxide and Molybdenum Dioxide Diacetylacetonate......Page 591
3.8.5.2 Ethanethiol and Aluminum Chloride......Page 592
3.8.6 References......Page 593
4.1.1 Introduction......Page 596
4.1.2 Oxidation with Alkaline Hydrogen Peroxide......Page 598
4.1.4 Oxidation with Trimethylamine N-Oxide......Page 600
4.1.5 Autoxidation......Page 601
4.1.6 Oxidation by Peracids......Page 602
4.1.7.1 Chromic Acid......Page 603
4.1.7.3 Pyridinium Chlorochromate......Page 604
4.1.9 Electrochemical Oxidation......Page 605
4.1.10 Oxidation by Carbonyl Compounds to Produce Alkenes......Page 606
4.1.12 Brominolysis of C-B Bonds......Page 607
4.1.14.1 Synthesis of Primary Amines......Page 609
4.1.15 Replacement of Boron by Sulfur or Selenium......Page 610
4.1.16 References......Page 611
4.2.1 Introduction......Page 615
4.2.2.2 Unactivated Carbon-Tin Bonds......Page 616
4.2.2.3 Allylic Stannanes......Page 618
4.2.2.4 Vinylstannanes......Page 622
4.2.2.5 gamma-Trialkylstannyl Alcohols; Oxidative 1,4-Fragmentation......Page 623
4.2.2.6 beta-Stannyl Hydrazones, Oximes and Carboxylic Acids......Page 630
4.2.3.1 pi- Allylpalladium Complexes......Page 631
4.2.3.2 Cyclopalladation-Oxidation......Page 632
4.2.4.1 Introduction......Page 633
4.2.4.2 Oxymercuration-Oxidative Demercuration......Page 634
4.2.4.3 Miscellaneous Oxidations......Page 639
4.2.5 References......Page 640
4.3.1 Introduction......Page 642
4.3.2.1 By Hydrosilylation......Page 643
4.3.2.2 From Functionalized Silanes......Page 647
4.3.3 Miscellaneous......Page 650
4.3.4 References......Page 651
4.4.2.1 Oxidation with Dimethyl Sulfoxide......Page 653
4.4.3 The Kröhnke Oxidation......Page 657
4.4.4 The Hass-Bender Reaction......Page 659
4.4.5.1 Pyridine N-Oxides and Derivatives......Page 661
4.4.5.2 N-Hydroxypyridones......Page 662
4.4.6 Chromium-Based Methods......Page 663
4.4.7.1 Silver Nitrate......Page 664
4.4.7.2 Other Metal Nitrates and Nitrites......Page 665
4.4.8 The Sommelet Oxidation......Page 666
4.4.9.1 Oxidation via the Pummerer Rearrangement......Page 667
4.4.9.2 Triflamides and Triflic Hydrazides......Page 668
4.4.10 References......Page 669
5.1.2.1 General......Page 671
5.1.2.2 Stereochemistry......Page 672
5.1.3.3 Regiochemistry......Page 673
5.1.3 Reaction Methods......Page 674
5.1.4.2 Competitive Baeyer-Villiger Reactions......Page 675
5.1.5.1 Acyclic Aliphatic Ketones......Page 676
5.1.5.3 Monocyclic and Spirocyclic Ketones......Page 678
5.1.5.4 Fused Ring Bicyclic and Polycyclic Ketones......Page 680
5.1.5.5 Bridged Bicyclic and Polycyclic Ketones......Page 682
5.1.5.8 Aryl- and Alkyl-Carbaldehydes......Page 684
5.1.6 Side Reactions......Page 685
5.1.7 References......Page 687
5.2.1 Introduction......Page 689
5.2.2.1 Mechanism and Stereochemistry......Page 690
5.2.2.2 Ketoximes......Page 691
5.2.3 Addition Reactions......Page 695
5.2.3.1 Intermolecular Reactions......Page 696
5.2.3.2 Intramolecular Reactions......Page 697
5.2.4.1 Carbon-Assisted Fragmentations......Page 698
5.2.4.2 Heteroatom-Assisted Fragmentations......Page 700
5.2.5 References......Page 701
5.3.2 Sodium Bismuthate......Page 703
5.3.3 Pentavalent Organobismuth Reagents......Page 704
5.3.4 Cerium(IV) Reagents......Page 705
5.3.8 Iodo Reagents......Page 706
5.3.10 Anodic Oxidation......Page 707
5.3.13.1 General Characteristics......Page 708
5.3.13.3 Applications in Organic Synthesis......Page 709
5.3.14 References......Page 715
5.4.1 Introduction......Page 717
5.4.2.2 Lead(IV) Carboxylates......Page 718
5.4.2.3 O-Acyl Oximes and O-Acyl Thiohydroxamates......Page 719
5.4.3.4 O-Acyl Benzophenone Oximes and t-Butyl Thiol......Page 720
5.4.3.6 Decarbonylation Methods......Page 721
5.4.4.2 1,4-Dicarboxylic Acids......Page 722
5.4.5.1 Acyl Hypohalites and Related Species......Page 723
5.4.5.3 O-Acyl Thiohydroxamates and Halogen Donor Solvents......Page 724
5.4.6 Decarboxylative Chalcogenation and Phosphorylation......Page 725
5.4.6.2 Selenation and Telluration......Page 726
5.4.7 Decarboxylative Oxygenation......Page 727
5.4.9 Decarboxylation with Subsequent C-C Bond Formation......Page 729
5.4.9.1 Addition to C-C Multiple Bonds......Page 730
5.4.9.2 Addition to C-Heteroatom Multiple Bonds......Page 731
5.4.9.3 Addition to Aromatic Systems......Page 732
5.4.10 References......Page 733
6.1.1 Introduction......Page 735
6.1.2.1 Primary Amines......Page 736
6.1.2.2 Hydrazones, Hydrazines and Hydroxylamines......Page 742
6.1.3.1 Secondary Amines......Page 745
6.1.3.2 Hydrazines and Hydroxylamines......Page 747
6.1.4.1 Formation of N-Oxides......Page 748
6.1.5.1 N-Oxidation of Heteroaromatic Amines......Page 749
6.1.5.3 Oxidation of Azo to Azoxy Compounds......Page 750
6.1.5.4 Oxidation of Oximes and Nitroso Compounds......Page 751
6.1.6 Oxidation of Phosphorus......Page 752
6.1.7 References......Page 753
6.2 Oxidation of Sulfur, Selenium and Tellurium......Page 757
6.2.2.1 Oxidation of Thiols to Disulfides by Molecular Oxygen and Chemical Reagents......Page 758
6.2.2.2 Oxidation of Sulfides to Sulfoxides by Chemical Reagents......Page 762
6.2.2.3 Oxidation of Sulfoxides to Sulfones by Chemical Reagents......Page 766
6.2.3.1 Oxidation of Selenols to Diselenides and Further Oxidized Species by Chemical Reagents......Page 769
6.2.3.2 Oxidation of Selenides to Selenoxides by Chemical Reagents......Page 770
6.2.3.3 Oxidation of Selenides and Selenoxides to Selenones......Page 773
6.2.4.1 Oxidation of Tellurols to Ditellurides and Further Oxidized Species by Chemical Reagents......Page 774
6.2.4.2 Oxidation of Tellurides to Telluroxides......Page 775
6.2.4.3 Oxidation of Tellurides to Tellurones......Page 776
6.2.5.1 Synthesis of Optically Active Sulfoxides by Chemical Oxidation......Page 777
6.2.5.2 Synthesis of Optically Active Sulfoxides by Biological Oxidation......Page 778
6.2.5.3 Synthesis of Optically Active Selenoxides by Chemical Oxidation......Page 779
6.2.6 References......Page 780
7.1 Oxidation by Electrochemical Methods......Page 788
7.1.1.2 Interface Reactions......Page 789
7.1.2.1 Apparatus......Page 790
7.1.2.2 Techniques......Page 791
7.1.3.1 Oxidation of Carbon-Hydrogen and Carbon-Carbon Single Bonds......Page 792
7.1.3.2 Oxidation of Unsaturated Systems......Page 793
7.1.3.3 Oxidation of Systems Bearing Lone Pairs of Electrons......Page 801
7.1.3.4 Oxidation of Anions......Page 804
7.1.4.1 Oxidation Using Mediators......Page 806
7.1.4.2 Formation of Active Species......Page 809
7.1.5 References......Page 810
7.2.1 Introduction......Page 813
7.2.2.1 Alkenes and Enols......Page 814
7.2.2.2 Allylic Alcohols......Page 819
7.2.2.3 Cyclopropanes and Cyclobutanes......Page 822
7.2.2.4 Miscellaneous Functional Group Rearrangements......Page 824
7.2.3 Oxidative Skeletal Rearrangement......Page 825
7.2.3.1 Alkenes and Enols......Page 826
7.2.3.2 Dienes......Page 830
7.2.3.4 Cyclopropanes and Cyclobutanes......Page 831
7.2.3.5 Miscellaneous Skeletal Rearrangements......Page 833
7.2.4 References......Page 834
7.3.1 Introduction......Page 836
7.3.2.4 Potassium Dichromate and Epoxidizing Agents......Page 838
7.3.3.2 Sodium Methoxide......Page 839
7.3.3.6 Periodates......Page 840
7.3.3.8 Chromium(VI)......Page 841
7.3.4.2 Thallium Trinitrate......Page 842
7.3.5 Conclusions......Page 843
7.3.6 References......Page 844
7.4 Electron-Transfer Oxidation......Page 846
7.4.1 Scope and Definitions......Page 847
7.4.2.1 Oxidation Potentials of Organic Compounds......Page 849
7.4.3 Generic Behavior of Radical Ions as Reactive Intermediates in Electron-Transfer Oxidation......Page 851
7.4.3.1 Chemistry of Organic Radical Cations......Page 854
7.4.3.2 The Follow-up Reactions of Organic Radical Cations......Page 857
7.4.3.3 Chemistry of Organic Radical Anions......Page 858
7.4.4 Thermal and Photochemical Activation of Electron-Transfer Oxidation......Page 859
7.4.4.1 Thermal Osmylation of Naphthalene, Anthracene and Phenanthrene......Page 860
7.4.4.3 Time-Resolved Spectra of Arene Radical Cations in Charge-Transfer Osmylation......Page 861
7.4.4.4 Common Features in Thermal and Charge-Transfer Osmylations......Page 862
7.4.4.5 Electron Transfer in the Charge-Transfer Osmylation of Arenes......Page 863
7.4.4.6 Electron Transfer as the Common Theme in Arene Osmylation......Page 864
7.4.5.1 EDA Complexes as Intermediates in Mercuration and Thallation. Comparison of Their Ground and CT Excited States......Page 865
7.4.5.2 Comparison of the Activation Barriers for Mercuration and Thallation......Page 866
7.4.5.4 The Relevance of Arene Radical Cations in Electrophilic Aromatic Substitution......Page 867
7.4.5.5 Electron Transfer versus Electrophilic Pathways for Aromatic Substitution......Page 869
7.4.6.1 Donor Radical Cations......Page 870
7.4.6.2 Acceptor Radical Anions......Page 879
7.4.7 References......Page 882
A......Page 887
B......Page 889
C......Page 894
D......Page 898
E......Page 901
F......Page 902
G......Page 904
H......Page 907
I......Page 911
J......Page 912
K......Page 913
L......Page 918
M......Page 921
N......Page 927
O......Page 929
P......Page 931
R......Page 933
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S......Page 936
T......Page 944
V......Page 947
W......Page 948
Y......Page 951
Z......Page 953
A......Page 954
B......Page 961
C......Page 965
D......Page 972
E......Page 975
F......Page 977
H......Page 978
I......Page 981
K......Page 982
M......Page 984
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