| |
| |
| |
| Alkylation of Nucleophilic Carbon Intermediates | |
| |
| |
| |
| Generation of Carbanions by Deprotonation | |
| |
| |
| |
| Regioselectivity and Stereoselectivity in Enolate Formation | |
| |
| |
| |
| Other Means of Generating Enolates | |
| |
| |
| |
| Alkylation of Enolates | |
| |
| |
| |
| Generation and Alkylation of Dianions | |
| |
| |
| |
| Medium Effects in the Alkylation of Enolates | |
| |
| |
| |
| Oxygen versus Carbon as the Site of Alkylation | |
| |
| |
| |
| Alkylation of Aldehydes, Esters, Amides, and Nitriles | |
| |
| |
| |
| The Nitrogen Analogs of Enols and Enolates--Enamines and Imine Anions | |
| |
| |
| |
| Alkylation of Carbon Nucleophiles by Conjugate Addition | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Reaction of Carbon Nucleophiles with Carbonyl Groups | |
| |
| |
| |
| Aldol Addition and Condensation Reactions | |
| |
| |
| |
| The General Mechanism | |
| |
| |
| |
| Mixed Aldol Condensations with Aromatic Aldehydes | |
| |
| |
| |
| Control of Regiochemistry and Stereochemistry of Mixed Aldol Reactions of Aliphatic Aldehydes and Ketones | |
| |
| |
| |
| Intramolecular Aldol Reactions and the Robinson Annulation | |
| |
| |
| |
| Addition Reactions of Imines and Iminium Ions | |
| |
| |
| |
| The Mannich Reaction | |
| |
| |
| |
| Amine-Catalyzed Condensation Reactions | |
| |
| |
| |
| Acylation of Carbanions | |
| |
| |
| |
| The Wittig and Related Reactions of Phosphorus-Stabilized Carbon Nucleophiles | |
| |
| |
| |
| Reactions of Carbonyl Compounds with [alpha]-Trimethylsilylcarbanions | |
| |
| |
| |
| Sulfur Ylides and Related Nucleophiles | |
| |
| |
| |
| Nucleophilic Addition--Cyclization | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Functional Group Interconversion by Nucleophilic Substitution | |
| |
| |
| |
| Conversion of Alcohols to Alkylating Agents | |
| |
| |
| |
| Sulfonate Esters | |
| |
| |
| |
| Halides | |
| |
| |
| |
| Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon | |
| |
| |
| |
| General Solvent Effects | |
| |
| |
| |
| Nitriles | |
| |
| |
| |
| Azides | |
| |
| |
| |
| Oxygen Nucleophiles | |
| |
| |
| |
| Nitrogen Nucleophiles | |
| |
| |
| |
| Sulfur Nucleophiles | |
| |
| |
| |
| Phosphorus Nucleophiles | |
| |
| |
| |
| Summary of Nucleophilic Substitution at Saturated Carbon | |
| |
| |
| |
| Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters | |
| |
| |
| |
| Interconversion of Carboxylic Acid Derivatives | |
| |
| |
| |
| Preparation of Reactive Reagents for Acylation | |
| |
| |
| |
| Preparation of Esters | |
| |
| |
| |
| Preparation of Amides | |
| |
| |
| Problems | |
| |
| |
| |
| Electrophilic Additions to Carbon--Carbon Multiple Bonds | |
| |
| |
| |
| Addition of Hydrogen Halides | |
| |
| |
| |
| Hydration and Other Acid-Catalyzed Additions of Oxygen Nucleophiles | |
| |
| |
| |
| Oxymercuration | |
| |
| |
| |
| Addition of Halogens to Alkenes | |
| |
| |
| |
| Electrophilic Sulfur and Selenium Reagents | |
| |
| |
| |
| Addition of Other Electrophilic Reagents | |
| |
| |
| |
| Electrophilic Substitution Alpha to Carbonyl Groups | |
| |
| |
| |
| Additions to Allenes and Alkynes | |
| |
| |
| |
| Addition at Double Bonds via Organoborane Intermediates | |
| |
| |
| |
| Hydroboration | |
| |
| |
| |
| Reactions of Organoboranes | |
| |
| |
| |
| Enantioselective Hydroboration | |
| |
| |
| |
| Hydroboration of Alkynes | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Reduction of Carbonyl and Other Functional Groups | |
| |
| |
| |
| Addition of Hydrogen | |
| |
| |
| |
| Catalytic Hydrogenation | |
| |
| |
| |
| Other Hydrogen-Transfer Reagents | |
| |
| |
| |
| Group III Hydride-Donor Reagents | |
| |
| |
| |
| Reduction of Carbonyl Compounds | |
| |
| |
| |
| Stereoselectivity of Hydride Reduction | |
| |
| |
| |
| Reduction of Other Functional Groups by Hydride Donors | |
| |
| |
| |
| Group IV Hydride Donors | |
| |
| |
| |
| Hydrogen-Atom Donors | |
| |
| |
| |
| Dissolving-Metal Reductions | |
| |
| |
| |
| Addition of Hydrogen | |
| |
| |
| |
| Reductive Removal of Functional Groups | |
| |
| |
| |
| Reductive Carbon--Carbon Bond Formation | |
| |
| |
| |
| Reductive Deoxygenation of Carbonyl Groups | |
| |
| |
| |
| Reductive Elimination and Fragmentation | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations | |
| |
| |
| |
| Cycloaddition Reactions | |
| |
| |
| |
| The Diels--Alder Reaction: General Features | |
| |
| |
| |
| The Diels--Alder Reaction: Dienophiles | |
| |
| |
| |
| The Diels--Alder Reaction: Dienes | |
| |
| |
| |
| Asymmetric Diels--Alder Reactions | |
| |
| |
| |
| Intramolecular Diels--Alder Reactions | |
| |
| |
| |
| Dipolar Cycloaddition Reactions | |
| |
| |
| |
| [2 + 2] Cycloadditions and Other Reactions Leading to Cyclobutanes | |
| |
| |
| |
| Photochemical Cycloaddition Reactions | |
| |
| |
| |
| [3,3] Sigmatropic Rearrangements | |
| |
| |
| |
| Cope Rearrangements | |
| |
| |
| |
| Claisen Rearrangements | |
| |
| |
| |
| [2,3] Sigmatropic Rearrangements | |
| |
| |
| |
| Ene Reactions | |
| |
| |
| |
| Unimolecular Thermal Elimination Reactions | |
| |
| |
| |
| Cheletropic Elimination | |
| |
| |
| |
| Decomposition of Cyclic Azo Compounds | |
| |
| |
| |
| [beta] Eliminations Involving Cyclic Transition States | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Organometallic Compounds of the Group I, II, and III Metals | |
| |
| |
| |
| Preparation and Properties | |
| |
| |
| |
| Reactions of Organomagnesium and Organolithium Compounds | |
| |
| |
| |
| Reactions with Alkylating Agents | |
| |
| |
| |
| Reactions with Carbonyl Compounds | |
| |
| |
| |
| Organic Derivatives of Group IIB and Group IIIB Metals | |
| |
| |
| |
| Organozinc Compounds | |
| |
| |
| |
| Organocadmium Compounds | |
| |
| |
| |
| Organomercury Compounds | |
| |
| |
| |
| Organoindium Reagents | |
| |
| |
| |
| Organolanthanide Reagents | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Reactions Involving the Transition Metals | |
| |
| |
| |
| Organocopper Intermediates | |
| |
| |
| |
| Preparation and Structure of Organocopper Reagents | |
| |
| |
| |
| Reactions Involving Organocopper Reagents and Intermediates | |
| |
| |
| |
| Reactions Involving Organopalladium Intermediates | |
| |
| |
| |
| Palladium-Catalyzed Nucleophilic Substitution and Alkylation | |
| |
| |
| |
| The Heck Reaction | |
| |
| |
| |
| Palladium-Catalyzed Cross Coupling | |
| |
| |
| |
| Carbonylation Reactions | |
| |
| |
| |
| Reactions Involving Organonickel Compounds | |
| |
| |
| |
| Reactions Involving Rhodium and Cobalt | |
| |
| |
| |
| Organometallic Compounds with [pi] Bonding | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Carbon--Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin | |
| |
| |
| |
| Organoboron Compounds | |
| |
| |
| |
| Synthesis of Organoboranes | |
| |
| |
| |
| Carbon--Carbon Bond-Forming Reactions of Organoboranes | |
| |
| |
| |
| Organosilicon Compounds | |
| |
| |
| |
| Synthesis of Organosilanes | |
| |
| |
| |
| Carbon--Carbon Bond-Forming Reactions | |
| |
| |
| |
| Organotin Compounds | |
| |
| |
| |
| Synthesis of Organostannanes | |
| |
| |
| |
| Carbon--Carbon Bond-Forming Reactions | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Reactions Involving Carbocations, Carbenes, and Radicals as Reactive Intermediates | |
| |
| |
| |
| Reactions Involving Carbocation Intermediates | |
| |
| |
| |
| Carbon-Carbon Bond Formation Involving Carbocations | |
| |
| |
| |
| Rearrangement of Carbocations | |
| |
| |
| |
| Related Rearrangements | |
| |
| |
| |
| Fragmentation Reactions | |
| |
| |
| |
| Reactions Involving Carbenes and Nitrenes | |
| |
| |
| |
| Structure and Reactivity of Carbenes | |
| |
| |
| |
| Generation of Carbenes | |
| |
| |
| |
| Addition Reactions | |
| |
| |
| |
| Insertion Reactions | |
| |
| |
| |
| Generation and Reactions of Ylides by Carbenoid Decomposition | |
| |
| |
| |
| Rearrangement Reactions | |
| |
| |
| |
| Related Reactions | |
| |
| |
| |
| Nitrenes and Related Intermediates | |
| |
| |
| |
| Rearrangements to Electron-Deficient Nitrogen | |
| |
| |
| |
| Reactions Involving Free-Radical Intermediates | |
| |
| |
| |
| Sources of Radical Intermediates | |
| |
| |
| |
| Introduction of Functionality by Radical Reactions | |
| |
| |
| |
| Addition Reactions of Radicals to Substituted Alkenes | |
| |
| |
| |
| Cyclization of Free-Radical Intermediates | |
| |
| |
| |
| Fragmentation and Rearrangement Reactions | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Aromatic Substitution Reactions | |
| |
| |
| |
| Electrophilic Aromatic Substitution | |
| |
| |
| |
| Nitration | |
| |
| |
| |
| Halogenation | |
| |
| |
| |
| Friedel-Crafts Alkylations and Acylations | |
| |
| |
| |
| Electrophilic Metalation | |
| |
| |
| |
| Nucleophilic Aromatic Substitution | |
| |
| |
| |
| Aryl Diazonium Ions as Synthetic Intermediates | |
| |
| |
| |
| Substitution by the Addition-Elimination Mechanism | |
| |
| |
| |
| Substitution by the Elimination-Addition Mechanism | |
| |
| |
| |
| Transition-Metal-Catalyzed Substitution Reactions | |
| |
| |
| |
| Aromatic Radical Substitution Reactions | |
| |
| |
| |
| Substitution by the S[subscript RN]1 Mechanism | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Oxidations | |
| |
| |
| |
| Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids | |
| |
| |
| |
| Transition-Metal Oxidants | |
| |
| |
| |
| Other Oxidants | |
| |
| |
| |
| Addition of Oxygen at Carbon-Carbon Double Bonds | |
| |
| |
| |
| Transition-Metal Oxidants | |
| |
| |
| |
| Epoxides from Alkenes and Peroxidic Reagents | |
| |
| |
| |
| Transformations of Epoxides | |
| |
| |
| |
| Reaction of Alkenes with Singlet Oxygen | |
| |
| |
| |
| Cleavage of Carbon-Carbon Double Bonds | |
| |
| |
| |
| Transition-Metal Oxidants | |
| |
| |
| |
| Oxonolysis | |
| |
| |
| |
| Selective Oxidative Cleavages at Other Functional Groups | |
| |
| |
| |
| Cleavage of Glycols | |
| |
| |
| |
| Oxidative Decarboxylation | |
| |
| |
| |
| Oxidation of Ketones and Aldehydes | |
| |
| |
| |
| Transition-Metal Oxidants | |
| |
| |
| |
| Oxidation of Ketones and Aldehydes by Oxygen and Peroxidic Compounds | |
| |
| |
| |
| Oxidation with Other Reagents | |
| |
| |
| |
| Allylic Oxidation | |
| |
| |
| |
| Transition-Metal Oxidants | |
| |
| |
| |
| Other Oxidants | |
| |
| |
| |
| Oxidations at Unfunctionalized Carbon | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| |
| Planning and Execution of Multistep Syntheses | |
| |
| |
| |
| Protective Groups | |
| |
| |
| |
| Hydroxyl-Protecting Groups | |
| |
| |
| |
| Amino-Protecting Groups | |
| |
| |
| |
| Carbonyl-Protecting Groups | |
| |
| |
| |
| Carboxylic Acid-Protecting Groups | |
| |
| |
| |
| Synthetic Equivalent Groups | |
| |
| |
| |
| Synthetic Analysis and Planning | |
| |
| |
| |
| Control of Stereochemistry | |
| |
| |
| |
| Illustrative Syntheses | |
| |
| |
| |
| Juvabione | |
| |
| |
| |
| Longifolene | |
| |
| |
| |
| Prelog-Djerassi Lactone | |
| |
| |
| |
| Taxol | |
| |
| |
| |
| Epothilone A | |
| |
| |
| |
| Solid-Phase Synthesis | |
| |
| |
| |
| Solid-Phase Synthesis of Polypeptides | |
| |
| |
| |
| Solid-Phase Synthesis of Oligonucleotides | |
| |
| |
| |
| Combinatorial Synthesis | |
| |
| |
| General References | |
| |
| |
| Problems | |
| |
| |
| References for Problems | |
| |
| |
| Index | |