Preface Acknowledgment and Personal Statemrnt Introduction Chapter 1. Alkylation of Enolates and Other Carbon Nucleophiles Introduction 1.1. Generation and Properties of Enolates and Other Stabilized Carbanions 1.1.1. Generation of Enolates by Deprotonation 1.1.2. Regioselectivity and Stereoselectivity in Enolate Formation from Ketones and Esters 1.1.3. Other Means of Generating Enolates 1.1.4. Solvent Effects on Enolate Structure and Reactivity 1.2. Alkylation of Enolates 1.2.1. Alkylation of Highly Stabilized Enolates 1.2.2. Alkylation of Ketone Enolates 1.2.3. Alkylation of Aldehydes,Esters,Carboxylic Acids,Amides,and Nitriles 1.2.4. Generation and Alkylation of Dianions 1.2.5. Intramolecular Alkylation of Enolates 1.2.6. Control of Enantioselectivity in Alkylation Reactions 1.3. The Nitrogen Analogs of Enols and Enolates:Enamines and Imine Anions General References Problems Chapter 2. Reactions of Carbon Nucleophiles with Carbonyl Compounds Introduction 2.1. Aldol Addition and Condensation Reactions 2.1.1. The General Mechanism 2.1.2. Control of Regio- and Stereoselectivity of Aldol Reactions of Aldehydes and Ketones 2.1.3. Aldol Addition Reactions of Enolates of Esters and Other Carbonyl Derivatives 2.1.4. The Mukaiyama Aldol Reaction 2.1.5. Control of Facial Selectivity in Aldol and Mukaiyama Aldol Reactions 2.1.6. Intramolecular Aldol Reactions and the Robinson Annulation 2.2. Addition Reactions of Imines and Iminium Ions 2.2.1. The Mannich Reaction 2.2.2. Additions to N-Acyl Iminium Ions 2.2.3. Amine-Catalyzed Condensation Reactions 2.3. Acylation of Carbon Nucleophiles 2.3.1. Claisen and Dieckmann Condensation Reactions 2.3.2. Acylation of Enolates and Other Carbon Nucleophiles 2.4. Olefination Reactions of Stabilized Carbon Nucleophiles 2.4.1. The Wittig and Related Reactions of Phosphorus-Stabilized Carbon Nucleophiles 2.4.2. Reactions of α-Trimethylsilylcarbanions with Carbonyl Compounds 2.4.3. The Julia Olefination Reaction 2.5. Reactions Proceeding by Addition-Cyclization 2.5.1. Sulfur Ylides and Related Nucleophiles 2.5.2. Nucleophilic Addition-Cyclization of α-Haloesters 2.6. Conjugate Addition by Carbon Nucleophiles 2.6.1. Conjugate Addition of Enolates 2.6.2. Conjugate Addition with Tandem Alkylation 2.6.3. Conjugate Addition by Enolate Equivalents 2.6.4. Control of Facial Selectivity in Conjugate Addition Reactions 2.6.5. Conjugate Addition of Organometallic Reagents 2.6.6. Conjugate Addition of Cyanide Ion General References Problems Chapter 3. Functional Group Interconversion by Substitution,Including Protection and Deproteetion Introduction 3.1. Conversion of Alcohols to Alkylating Agents 3.1.1. Sulfonate Esters 3.1.2. Halides 3.2. Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon 3.2.1. General Solvent Effects 3.2.2. Nitriles 3.2.3. Oxygen Nucleophiles 3.2.4. Nitrogen Nucleophiles 3.2.5. Sulfur Nucleophiles 3.2.6. Phosphorus Nucleophiles 3.2.7. Summary of Nucleophilic Substitution at Saturated Carbon 3.3. Cleavage of Carbon-Oxygen Bonds in Ethers and Esters 3.4. Interconversion of Carboxylic Acid Derivatives 3.4.1. Acylation of Alcohols 3.4.2. Fischer Esterification 3.4.3. Preparation of Amides 3.5. Installation and Removal of Protective Groups 3.5.1. Hydroxy-Protecting Groups 3.5.2. Amino-Protecting Groups 3.5.3. Carbonyl-Protecting Groups 3.5.4. Carboxylic Acid-Protecting Groups Problems Chapter 4. Electrophilic Additions to Carbon-Carbon Multiple Bonds Introduction 4.1. Electrophilic Addition to Alkenes 4.1.1. Addition of Hydrogen Halides 4.1.2. Hydration and Other Acid-Catalyzed Additions of Oxygen Nucleophiles 4.1.3. Oxymercuration-Reduction 4.1.4. Addition of Halogens to Alkenes 4.1.5. Addition of Other Electrophilic Reagents 4.1.6. Addition Reactions with Electrophilic Sulfur and Selenium Reagents 4.2. Electrophilic Cyclization 4.2.1. Halocyclization 4.2.2. Sulfenylcyclization and Selenenylcyclization 4.2.3. Cyclization by Mercuric Ion 4.3. Electrophilic Substitution α to Carbonyl Groups 4.3.1. Halogenation α to Carbonyl Groups 4.3.2. Sulfenylation and Selenenylation α to Carbonyl Groups 4.4. Additions to Allenes and Alkynes 4.5. Addition at Double Bonds via Organoborane Intermediates 4.5.1. Hydroboration 4.5.2. Reactions of Organoboranes 4.5.3. Enantioselective Hydroboration 4.5.4. Hydroboration of Alkynes 4.6. Hydroalumination, Carboalumination, Hydrozirconation,and Related Reactions General References Problems Chapter 5. Reduction of Carbon-Carbon Multiple Bonds,Carbonyl Groups,and Other Functional Groups Introduction 5.1. Addition of Hydrogen at Carbon-Carbon Multiple Bonds 5.1.1. Hydrogenation Using Heterogeneous Catalysts 5.1.2. Hydrogenation Using Homogeneous Catalysts 5.1.3. Enantioselective Hydrogenation 5.1.4. Partial Reduction of Alkynes 5.1.5. Hydrogen Transfer from Diimide 5.2. Catalytic Hydrogenation of Carbonyl and Other Functional Groups 5.3. Group III Hydride-Donor Reagents 5.3.1. Comparative Reactivity of Common Hydride Donor Reagents 5.3.2. Stereoselectivity of Hydride Reduction 5.3.3. Enantioselective Reduction of Carbonyl Compounds 5.3.4. Reduction of Other Functional Groups by Hydride Donors 5.4. Group IV Hydride Donors 5.4.1. Reactions Involving Silicon Hydrides 5.4.2. Hydride Transfer from Carbon 5.5. Reduction Reactions Involving Hydrogen Atom Donors 5.6. Dissolving-Metal Reductions 5.6.1. Addition of Hydrogen 5.6.2. Reductive Removal of Functional Groups 5.6.3. Reductive Coupling of Carbonyl Compounds 5.7. Reductive Deoxygenation of Carbonyl Groups 5.7.1. Reductive Deoxygenation of Carbonyl Groups to Methylene 5.7.2. Reduction of Carbonyl Compounds to Alkenes 5.8. Reductive Elimination and Fragmentation Problems Chapter 6. Concerted Cyeloadditions,Unimoleeular Rearrangements,and Thermal Eliminations Introduction 6.1. Diels-Alder Reactions 6.1.1. The Diels-Alder Reaction: General Features 6.1.2. Substituent Effects on the Diels-Alder Reaction 6.1.3. Lewis Acid Catalysis of the Diels-Alder Reaction 6.1.4. The Scope and Synthetic Applications of the Diels-Alder Reaction 6.1.5. Diastereoselective Diels-Alder Reactions Using Chiral Auxiliaries 6.1.6. Enantioselective Catalysts for Diels-Alder Reactions 6.1.7. Intramolecular Diels-Alder Reactions 6.2. 1,3-Dipolar Cycloaddition Reactions 6.2.1. Regioselectivity and Stereochemistry 6.2.2. Synthetic Applications of Dipolar Cycloadditions 6.2.3. Catalysis of 1,3-Dipolar Cycloaddition Reactions 6.3. [2 + 2] Cycloadditions and Related Reactions Leading to Cyclobutanes 6.3.1. Cycloaddition Reactions of Ketenes and Alkenes 6.3.2. Photochemical Cycloaddition Reactions 6.4. [3,3]-Sigmatropic Rearrangements 6.4.1. Cope Rearrangements 6.4.2. Claisen and Modified Claisen Rearrangements 6.5. [2,3]-Sigmatropic Rearrangements 6.5.1. Rearrangement of Allylic Sulfoxides, Selenoxides,and Amine Oxides 6.5.2. Rearrangement of Allylic Sulfonium and Ammonium Ylides 6.5.3. Anionic Wittig and Aza-Wittig Rearrangements 6.6. Unimolecular Thermal Elimination Reactions 6.6.1. Cheletropic Elimination 6.6.2. Decomposition of Cyclic Azo Compounds 6.6.3. [3-Eliminations Involving Cyclic Transition Structures Problems Chapter 7. Organometallie Compounds of Group I and II Metals Introduction 7.1. Preparation and Properties of Organomagnesium and Organolithium Reagents 7.1.1. Preparation and Properties of Organomagnesium Reagents 7.1.2. Preparation and Properties of Organolithium Compounds 7.2. Reactions of Organomagnesium and Organolithium Compounds 7.2.1. Reactions with Alkylating Agents 7.2.2. Reactions with Carbonyl Compounds 7.3. Organometallic Compounds of Group IIB and IIIB Metals 7.3.1. Organozinc Compounds 7.3.2. Organocadmium Compounds 7.3.3. Organomercury Compounds 7.3.4. Organoindium Reagents 7.4. Organolanthanide Reagents General References Problems Chapter 8. Reactions Involving Transition Metals Introduction 8.1. Organocopper Intermediates 8.1.1. Preparation and Structure of Organocopper Reagents 8.1.2. Reactions Involving Organocopper Reagents and Intermediates 8.2. Reactions Involving Organopalladium Intermediates 8.2.1. Palladium-Catalyzed Nucleophilic Addition and Substitution 8.2.2. The Heck Reaction 8.2.3. Palladium-Catalyzed Cross Coupling 8.2.4. Carbonylation Reactions 8.3. Reactions Involving Other Transition Metals 8.3.1. Organonickel Compounds 8.3.2. Reactions Involving Rhodium and Cobalt 8.4. The Olefin Metathesis Reaction 8.5. Organometallic Compounds with w-Bonding General References Problems Chapter 9. Carbon-Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin Introduction 9.1. Organoboron Compounds 9.1.1. Synthesis of Organoboranes 9.1.2. Carbonylation and Other One-Carbon Homologation Reactions 9.1.3. Homologation via α-Halo Enolates 9.1.4. Stereoselective Alkene Synthesis 9.1.5. Nucleophilic Addition of Allylic Groups from Boron Compounds 9.2. Organosilicon Compounds 9.2.1. Synthesis of Organosilanes 9.2.2. General Features of Carbon-Carbon Bond-Forming Reactions of Organosilicon Compounds 9.2.3. Addition Reactions with Aldehydes and Ketones 9.2.4. Reaction with Iminium Ions 9.2.5. Acylation Reactions 9.2.6. Conjugate Addition Reactions 9.3. Organotin Compounds 9.3.1. Synthesis of Organostannanes 9.3.2. Carbon-Carbon Bond-Forming Reactions 9.4. Summary of Stereoselectivity Patterns General References Problems Chapter 10. Reactions Involving Carboeations,Carbenes,and Radicals as Reactive Intermediates Introduction 10.1. Reactions and Rearrangement Involving Carbocation Intermediates 10.1.1. Carbon-Carbon Bond Formation Involving Carbocations 10.1.2. Rearrangement of Carbocations 10.1.3. Related Rearrangements 10.1.4. Fragmentation Reactions 10.2. Reactions Involving Carbenes and Related Intermediates 10.2.1. Reactivity of Carbenes 10.2.2. Generation of Carbenes 10.2.3. Addition Reactions 10.2.4. Insertion Reactions 10.2.5. Generation and Reactions of Ylides by Carbenoid Decomposition 10.2.6. Rearrangement Reactions 10.2.7. Related Reactions 10.2.8. Nitrenes and Related Intermediates 10.2.9. Rearrangements to Electron-Deficient Nitrogen 10.3. Reactions Involving Free Radical Intermediates 10.3.1. Sources of Radical Intermediates 10.3.2. Addition Reactions of Radicals with Substituted Alkenes 10.3.3. Cyclization of Free Radical Intermediates 10.3.4. Additions to C=N Double Bonds 10.3.5. Tandem Radical Cyclizations and Alkylations 10.3.6. Fragmentation and Rearrangement Reactions 10.3.7. Intramolecular Functionalization by Radical Reactions Problems Chapter 11. Arornatie Substitution Reactions Introduction 11.1. Electrophilic Aromatic Substitution 11.1.1. Nitration 11.1.2. Halogenation 11.1.3. Friedel-Crafts Alkylation 11.1.4. Friedel-Crafts Acylation 11.1.5. Related Alkylation and Acylation Reactions 11.1.6. Electrophilic Metallation 11.2. Nucleophilic Aromatic Substitution 11.2.1. Aryl Diazonium Ions as Synthetic Intermediates 11.2.2. Substitution by the Addition-Elimination Mechanism 11.2.3. Substitution by the Elimination-Addition Mechanism 11.3. Transition Metal-Catalyzed Aromatic Substitution Reactions 11.3.1. Copper-Catalyzed Reactions 11.3.2. Palladium-Catalyzed Reactions 11.4. Aromatic Substitution Reactions Involving Radical Intermediates 11.4.1. Aromatic Radical Substitution 11.4.2. Substitution by the SRN1 Mechanism Problems Chapter 12. Oxidations Introduction 12.1. Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids 12.1.1. Transition Metal Oxidants 12.1.2. Other Oxidants 12.2. Addition of Oxygen at Carbon-Carbon Double Bonds 12.2.1. Transition Metal Oxidants 12.2.2. Epoxides from Alkenes and Peroxidic Reagents 12.2.3. Subsequent Transformations of Epoxides 12.3. Allylic Oxidation 12.3.1. Transition Metal Oxidants 12.3.2. Reaction of Alkenes with Singlet Oxygen 12.3.3. Other Oxidants 12.4. Oxidative Cleavage of Carbon-Carbon Double Bonds 12.4.1. Transition Metal Oxidants 12.4.2. Ozonolysis 12.5. Oxidation of Ketones and Aldehydes 12.5.1. Transition Metal Oxidants 12.5.2. Oxidation of Ketones and Aldehydes by Oxygen and Peroxidic Compounds 12.5.3. Oxidation with Other Reagents 12.6. Selective Oxidative Cleavages at Functional Groups 12.6.1. Cleavage of Glycols 12.6.2. Oxidative Decarboxylation 12.7. Oxidations at Unfunctionalized Carbon Problems Chapter 13. Multistep Syntheses Introduction 13.1. Synthetic Analysis and Planning 13.1.1. Retrosynthetic Analysis 13.1.2. Synthetic Equivalent Groups 13.1.3. Control of Stereochemistry 13.2. Illustrative Syntheses 13.2.1. Juvabione 13.2.2. Longifolene 13.2.3. Prelog-Djerassi Lactone 13.2.4. Baccatin III and Taxol 13.2.5. Epothilone A 13.2.6. Discodermolide 13.3. Solid Phase Synthesis 13.3.1. Solid Phase Polypeptide Synthesis 13.3.2. Solid Phase Synthesis of Oligonucleotides 13.4. Combinatorial Synthesis General References Problems References Index
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