Comprehensive Organic Reactions in Aqueous Media Book

Preface to the Second Edition     XV
Introduction     1
The Structure and Forms of Water     3
Properties of Water     4
Solvation     6
Hydrophobic Effect     6
Salt Effect     8
Water Under Extreme Conditions     9
References     13
Alkanes     15
Oxygenation of Alkanes     15
Halogenation of Alkanes     20
Formation of Carbon-Carbon Bonds     20
D/H Exchange of Alkanes in Water     21
References     22
Alkenes     25
Reduction     25
Hydrogenation     25
Electrophilic Additions     28
Reaction with Halogen     28
Reaction with Hydrogen Halides     28
Addition of Water     29
Oxymercuration/Oxymetalation     29
Epoxidation     30
Dihydroxylation and Hydroxylamination     35
Wacker's Oxidation     40
Oxidative C=C Bond Cleavage     43
C-C Bond Formations     46
Radical Reactions of Alkenes     47
Radical Polymerization of Alkenes     47
Radical Additions     48
Radical Cyclization     49
Carbene Reactions     50
The Generation of Carbenes in Aqueous Medium     50
The Stability of Carbenes     50
The Reaction of Carbenes with Alkenes in Aqueous Medium     51
Alkene Isomerization     52
Transition-Metal Catalyzed C-C Formation Reactions     53
Polymerizations     53
Heck Reactions and Related Vinylation/Arylation     54
Hydrovinylation     56
Reaction with Arenes     56
Hydroformylation     57
Reaction with Alkynes     58
Carbonylation     60
Cycloaddition Reactions of Alkenes     60
Olefin Metathesis     60
Ring-Opening Metathesis Polymerization (ROMP)     61
Ring-Closing Metathesis (RCM)     62
Reaction of Allylic C-H Bond     64
Allylic Oxidation     64
C-C Bond Formations     65
References     66
Alkynes     77
Reaction of Terminal Alkynes     77
Alkyne Oxidative Dimerization     77
Alkyne-Alkyne Addition     78
Reaction of Alkynes with Organic Halides     81
Reaction of Alkynes with Carbonyl Compounds     93
Reaction of Alkynes with C=N Compounds     94
Conjugate Addition with Terminal Alkynes     97
Additions of C[Xi]C bonds     98
Reduction     98
Addition of Water     98
Addition of Alcohols and Amines     100
Hydrosilation and Hydrometalations     102
Addition of Aryls     104
Carbonylation of Internal Alkynes     107
Other Additions to Alkynes     109
Transition-Metal Catalyzed Cycloadditions     109
Pauson-Khand-Type Reactions     109
[2 + 2 + 2] Cyclotrimerization     111
[2 + 2 + 2] Alkyne-Nitrile Cyclotrimerization     114
[3 + 2] 1,3-Dipolar Cycloaddition     114
[4 + 2] Cycloaddition     118
[5 + 2] Cycloaddition     119
Other Cycloadditions     119
Other Reactions     121
References     121
Alcohols, Phenols, Ethers, Thiols, and Thioethers     129
Oxidation of Alcohols     129
Diol Cleavage     134
Substitutions/Elimination     134
Addition of Alcohols, Phenols, and Thiols to Alkene and Alkyne Bonds     137
Addition of Alcohols to C=O Bonds: Esterification and Acetal Formations     137
Reaction of Ethers and Cyclic Ethers     138
Ethers and Cyclic Ethers     138
Reactions of Epoxides in Water and "Click Chemistry"     139
Reaction of Sulfur Compounds     141
Oxidation of Thiols and Thioethers     141
Reduction of Disulfides     142
Native Chemical Ligation for Peptide Synthesis     143
Other Reactions     143
References     144
Organic Halides     151
General     151
Redaction     151
Elimination Reactions     154
Nucleophilic Substitutions     154
Substituted by Heteroatoms     154
Carbon-Carbon Bond Formations     158
Reductive Coupling     161
Wurtz-Type Coupling     161
Ullmann-Type Coupling and Related Reactions     163
Carbonylation of Organic Halides     164
Carbonylation of Alkyl Halides     164
Carbonylation of Allylic and Benzylic Halides     165
Carbonylation of Aryl Halides     165
Transition-Metal Catalyzed Coupling Reactions     166
The Heck Coupling     166
The Suzuki Coupling      167
The Stille Coupling     172
Other Transition-Metal Catalyzed Couplings     173
References     174
Aromatic Compounds     181
General     181
Substitution Reactions     182
Electrophilic Substitutions     182
Friedel-Crafts C-C Bond Formations     183
Other Substitution Reactions     189
Oxidation Reactions     190
Simple Oxidation     190
Oxidative Coupling     191
Reductions     192
References     193
Aldehdye and Ketones     197
Reduction     197
Hydrogenation     197
Other Reductions     198
Oxidation     204
Nucleophilic Addition: C-C Bond Formation     206
Allylation     206
Propargylation     238
Cyclopentadienylation     242
Benzylation     242
Arylation/Vinylation     244
Alkynylation     246
Alkylation     246
Reformatsky-Type Reaction     246
Direct Aldol Reaction     248
Mukaiyama Aldol Reaction     252
Hydrogen Cyanide Addition      258
Wittig Reactions     259
Pinacol Coupling     261
Other Reactions (Halogenation and Oxidation of [alpha]-H)     262
References     263
Carboxylec Acids and Derivatives     279
General     279
Reaction of [alpha]-Hydrogen     279
Reduction     279
Carboxylic Acids     280
Esterification/Amidation     280
Decarboxylation     287
Carboxylic Acid Derivatives     287
Esters and Thiol Esters     287
Acid Halides and Anhydrides     288
Amides     289
Nitriles     289
References     290
Conjugated Carbonyl Compounds     293
Reduction     293
Hydrogenation     293
Asymmetric Hydrogenation     295
Reduction by Other Methods     296
Epoxidation, Dihydroxylation, Hydroxyamination     297
Conjugate Addition: Heteroatom     298
C-C Bond Formation     301
Addition of Hydrogen Cyanide     302
Addition of [alpha]-Carbonyl Compounds     302
Addition of Allyl Groups     304
Addition of Alkyl Groups      305
Addition of Vinyl and Aryl Groups     307
Addition of Alkynyl Groups     310
Other Conjugate Additions     310
Other Reactions     310
Reductive Coupling     310
Baylis-Hillman Reactions     311
[gamma]-Addition of Alkynoates     314
References     315
Nitrogen Compounds     321
Amines     321
Alkylation     321
Diazotization and Nitrosation     322
Oxidation     323
Reaction with Carbonyl Compounds     326
Imines     327
Reductions     327
Nucleophilic Additions     329
Reductive Coupling     342
Diazo Compounds     343
Substitution     343
Reduction     343
Cyclopropanation     344
Coupling Reaction     346
Azides     346
Substitution     346
Click Chemistry     347
Nitro Compounds     349
References     349
Pericyclic Reactions     355
Introduction     355
Diels-Alder Reactions     357
Lewis-Acid Catalysis      360
Asymmetric Diels-Alder Reactions     367
Theoretical and Mechanistic Studies     371
Synthetic Applications     374
Hetero-Diels-Alder Reactions     382
Asymmetric Hetero-Diels-Alder Reactions     388
Other Cyclization Reactions     390
Sigmatropic Rearrangements     392
Claisen Rearrangements     392
Cope Rearrangements     397
Photochemical Cycloaddition Reactions     398
References     399
Index     409