Advanced Organic Synthesis

Title page\r......Page 1
Contents......Page 3
Preface......Page 8
I. FUNCTIONAL GROUP MODIFICATIONS......Page 10
I. Chromium Trioxide Oxidation......Page 11
II. Periodate-Permanganate Cleavage of Olefins......Page 13
III. Free Radical Oxidation of an Allylic Position......Page 15
IV. Epoxidation of OIefins......Page 16
V. Baeyer-Villiger Oxidation of Ketones......Page 17
VII. Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime......Page 19
VIII. Oxidation of Ethers to Esters......Page 20
IX. Partial Oxidation of an Aliphatic Side Chain......Page 21
X. Bisdecarboxylation with Lead Tetraacetate......Page 22
XI. Oxidation with Selenium Dioxide......Page 23
I. Reduction by Lithium Aluminum Hydride......Page 26
II. Mixed Hydride Reduction (5)......Page 28
III. Reduction with Iridium-Containing Catalysts......Page 30
IV. Reduction of Conjugated Alkenes with Chromium (II) Sulfate......Page 31
I. Reduction by Lithium-Amine......Page 33
II. Reduction by Lithium-Ethylenediamine......Page 34
III. Reduction of alpha,beta-Unsaturated Ketones by Lithium-Ammonia......Page 35
IV. Reduction of a,p-Unsaturated Ketones in Hexamethylphosphoric Triamide......Page 36
V. Reduction of an alpha,beta-Unsaturated gamma-Diketone with Zinc......Page 37
4. Hydroboration......Page 39
I. Hydroboration of Olefins as a Route to Alcohols......Page 40
II. Selective Hydroborations Using Bis(3-methyl-2-butyl)borane (BMB)......Page 43
III. Purification of a Mixture of A9-10- and delta1(9)-Octalins......Page 45
I. Hydrogenation over Platinum Catalyst (2d)......Page 47
II. Low-Pressure Hydrogenation of Phenols over Rhodium Catalysts......Page 48
III. cis-4-Hydroxycyclohexanecarboxylic Acid from p-Hydroxybenzoic Acid......Page 49
IV. 3-Isoquinuclidone from p-Aminobenzoic Acid......Page 50
V. Homogeneous Catalytic Hydrogenation......Page 51
I. Halides from Alcohols by Triphenylphosphine-Carbon Tetrahalide......Page 53
II. Halides from Alcohols and Phenols by Triphenylphosphine Dihalide......Page 54
III. Allylic and Benzylic Bromination with N-Bromosuccinimide......Page 56
IV. alfa-Bromination of Ketones and Dehydrobromination......Page 57
V. Stereospecific Synthesis of trans-4-HaIocyclohexanols......Page 59
I. Methylenecyclohexane by Pyrolysis of an Amine Oxide......Page 62
II. The Wolff-Kishner Reduction......Page 63
IV. Boron Trifluoride Catalyzed Hydrolysis of Nitriles......Page 64
V. Bridged Sulfides by Addition of Sulfur Dichloride to Dienes......Page 65
VI. Methylation by Diazomethane......Page 66
VII. Oxymercuration: A Convenient Route to Markovnikov Hydration of Olefins......Page 68
VIII. Esterification of Tertiary Alcohols......Page 70
IX. Ketalization......Page 71
X. Half-Esterification of a Diol......Page 72
XI. Substitution on Ferrocene......Page 73
XII. Demethylation of Aryl Methyl Ethers by Boron Tribromide......Page 74
II. SKELETAL MODIFICATIONS......Page 76
I. 3,6-Diphenyl-4,5-cyclohexenedicarboxylic Anhydride......Page 77
II. Reactions with Butadiene......Page 78
III. Catalysis by Aluminum Chloride......Page 80
IV. Generation of Dienes from Diones......Page 81
V. Reactions with Cyclopentadiene......Page 83
I. Preparation of the Morpholine Enamine of Cyclohexanone......Page 86
II. Acylation of Enamines......Page 87
III. Enamines as Michael Addition Reagents......Page 88
IV. Reactions of Enamines with beta-Propiolactone......Page 89
V. Reactions of Enamines with Acrolein......Page 90
I. Ketones as Enolates: Carbethoxylation of Cyclic Ketones......Page 93
II. Esters as Enolates: 1,4-Cyclohexanedione and Meerwein\'s Ester......Page 96
III. Methylsulfinyl Carbanion as a Route to Methyl Ketones......Page 98
IV. Cyclization with Diethyl Malonate......Page 102
V. Carboxylations with Magnesium Methyl Carbonate (MMC)......Page 103
VI. Alkylation of beta-Ketoesters......Page 105
VIl. The Robinson Annelation Reaction......Page 107
I. Benzyl-Containing Ylides......Page 110
II. Alkyl Ylides Requiring n-Butyl Lithium......Page 111
III. Methylsulfinyl Carbanion in the Generation of Ylides......Page 112
IV. The Wittig Reaction Catalyzed by Ethylene Oxide......Page 113
V. Cyclopropylidene Derivatives via the Wittig Reaction......Page 114
I. Trialkylcarbinols from Trialkylboranes and Carbon Monoxide......Page 117
II. Dialkylketones from Trialkylboranes and Carbon Monoxide-Water......Page 118
III. The Reaction of Trialkylboranes with Methyl Vinyl Ketone and Acrolein......Page 120
IV. The Reaction of Trialkylboranes with Ethyl Bromoacetate......Page 121
I. Carbene Addition by the Zinc-Copper Couple......Page 122
II. Dibromocarbenes......Page 123
III. Dihalocarbenes from Phenyl(trihalomethyl)mercury Compounds......Page 125
I. Generation of Sodium Acetylide in Liquid Ammonia......Page 127
II. The Generation of Sodium Acetylide in Tetrahydrofuran......Page 129
III. The Generation of Sodium Acetylide via Dimsylsodium......Page 130
I. Acid Catalyzed Rearrangement of Saturated Hydrocarbons......Page 132
II. Photolytic Ring Contraction......Page 133
HI. Isomerization of 1-Ethynylcyclohexanol: Three Methods......Page 135
V. Oxidative Rearrangement of beta-Diketones......Page 136
VI. Base Catalyzed Rearrangement of 4-Benzoyloxycyclohexanone......Page 137
VII. Allenes from 1,1-Dihalocyclopropanes by Methyllithium......Page 138
I. Carboxylation of Carbonium Ions......Page 140
II. Paracyclophane via a 1,6-Hofmann Elimination......Page 142
III. Diphenylcyclopropenone from Commercial Dibenzyl Ketone......Page 143
IV. Phenylcyclopropane from Cinnamaldehyde......Page 145
V. Conversion of Alkyl Chlorides to Nitriles in DMSO......Page 146
VI. Photolytic Addition of Formamide to Olefins......Page 147
VII. Intermolecular Dehydrohalogenation......Page 148
VIII. Ring Enlargement with Diazomethane......Page 149
IX. Conjugate Addition of Grignard Reagents......Page 150
X. Dimethyloxosulfonium Methylide in Methylene Insertions......Page 151
XI. Acylation of a Cycloalkane: Remote Functionalization......Page 153
XII. The Modified Hunsdiecker Reaction......Page 155
I. Derivatives of Adamantane......Page 157
II. Percarboxylic Acids......Page 159
III. Diazomethane......Page 161
IV. Trichloroisocyanuric Acid......Page 162
Appendix 1. Examples of Multistep Syntheses*......Page 164
Appendix 2. Sources of Organic Reagents......Page 167
Appendix 3. Introduction to the Techniques of Synthesis......Page 172
Subject Index......Page 195