Advanced Organic Chemistry

The main theme of Part B is the description of synthetically useful reactions and the illustration of their application. We have attempted to update the material to reflect the most important advances in synthetic methodology. Because of the extensive developments in the use of organic derivatives of transition metals, as well as of silicon and tin, we have separated the organometallic material into three chapters. Chapter 7 emphasizes organolithium and organomagnesium chemistry and also considers the group lIB metals. Transition metal chemistry is discussed in Chapter 8, with emphasis on copper and palladium intermediates. In Chapter 9, the carbon-carbon bond-forming reactions of organoboranes, silanes, and stannanes are discussed. The increased importance of free-radical reactions in synthesis has led to the incorporation of a section on radical reactions into Chapter 10, in which carbocations, carbenes, and nitrenes are also discussed. Certainly a major advance in synthetic chemistry during the 1980s was the development of methods for enantioselective synthesis. We have increased the level of attention to stereochemistry in the discussion of many reactions. In areas in which new stereoselective methods have been well developed, such as in aldol condensa­ tions, hydroboration, catalytic reduction, and epoxidation, we discuss these methods. The final chapter discusses some of the general issues which must be addressed in multistep synthesis and provides some illustrative syntheses which can provide the basis for more detailed study of this aspect of synthetic chemistry.

Contenu

of Part B.- 1. Alkylation of Nucleophilic Carbon. Enolates and Enamines.- 1.1. Generation of Carbanions by Deprotonation.- 1.2. Regioselectivity and Stereoselectivity in Enolate Formation.- 1.3. Other Means of Generating Enolates.- 1.4. Alkylation of Enolates.- 1.5. Generation and Alkylation of Dianions.- 1.6. Medium Effects in the Alkylation of Enolates.- 1.7. Oxygen versus Carbon as the Site of Alkylation.- 1.8. Alkylation of Aldehydes, Esters, Amides, and Nitriles.- 1.9. The Nitrogen Analogs of Enols and Enolates-Enamines and Imine Anions.- 1.10. Alkylation of Carbon Nucleophiles by Conjugate Addition.- General References.- Problems.- 2. Reactions of Carbon Nucleophiles with Carbonyl Groups.- 2.1. Aldol Condensation.- 2.1.1. The General Mechanism.- 2.1.2. Mixed Aldol Condensations with Aromatic Aldehydes.- 2.1.3. Control of Regiochemistry and Stereochemistry of Mixed Aldol Condensations of Aliphatic Aldehydes and Ketones.- 2.1.4. Intramolecular Aldol Condensations and the Robinson Annulation.- 2.2. Condensation Reactions of Imines and Iminium Ions.- 2.2.1. The Mannich Reaction.- 2.2.2. Amine-Catalyzed Condensation Reactions.- 2.3. Acylation of Carbanions.- 2.4. The Wittig and Related Reactions.- 2.5. Reactions of Carbonyl Compounds with ?-Trimethylsilyl Carbanions.- 2.6. Sulfur Ylides and Related Nucleophiles.- 2.7. Nucleophilic Addition-Cyclization.- General References.- Problems.- 3. Functional Group Interconversion by Nucleophilic Substitution.- 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. Azides.- 3.2.4. Alkylation of Amines and Amides.- 3.2.5. Oxygen Nucleophiles.- 3.2.6. Sulfur Nucleophiles.- 3.2.7. Phosphorus Nucleophiles.- 3.2.8. Summary of Nucleophilic Substitution at Saturated Carbon.- 3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters.- 3.4. Interconversion of Carboxylic Acid Derivatives.- 3.4.1. Preparation of Reaction Reagents for Acylation.- 3.4.2. Preparation of Esters.- 3.4.3. Preparation of Amides.- Problems.- 4. Electrophilic Additions to Carbon-Carbon Multiple Bonds.- 4.1. Addition of Hydrogen Halides.- 4.2. Hydration and Other Acid-Catalyzed Additions.- 4.3. Oxymercuration.- 4.4. Addition of Halogens to Alkenes.- 4.5. Electrophilic Sulfur and Selenium Reagents.- 4.6. Addition of Other Electrophilic Reagents.- 4.7. Electrophilic Substitution Alpha to Carbonyl Groups.- 4.8. Additions to Alienes and Alkynes.- 4.9. Addition at Double Bonds via Organoboranes.- 4.9.1. Hydroboration.- 4.9.2. Reactions of Organoboranes.- 4.9.3. Enantioselective Hydroboration.- 4.9.4. Hydroboration of Alkynes.- General References.- Problems.- 5. Reduction of Carbonyl and Other Functional Groups.- 5.1. Addition of Hydrogen.- 5.1.1. Catalytic Hydrogenation.- 5.1.2. Other Hydrogen-Transfer Reagents.- 5.2. Group III Hydride-Donor Reagents.- 5.2.1. Reduction of Carbonyl Compounds.- 5.2.2. Reduction of Other Functional Groups by Hydride Donors.- 5.3. Group IV Hydride Donors.- 5.4. Hydrogen Atom Donors.- 5.5. Dissolving-Metal Reductions.- 5.5.1. Addition of Hydrogen.- 5.5.2. Reductive Removal of Functional Groups.- 5.5.3. Reductive Carbon-Carbon Bond Formation.- 5.6. Reductive Deoxygenation of Carbonyl Groups.- General References.- Problems.- 6. Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations.- 6.1. Cycloaddition Reactions.- 6.1.1. The Diels-Alder Reaction: General Features.- 6.1.2. The Diels-Alder Reaction: Dienophiles.- 6.1.3. The Diels-Alder Reaction: Dienes.- 6.1.4. Intramolecular Diels-Alder Reactions.- 6.2. Dipolar Cycloaddition Reactions.- 6.3. [2 +2] Cycloadditions and Other Reactions Leading to Cyclobutanes.- 6.4. Photochemical Cycloaddition Reactions.- 6.5. [3,3]-Sigmatropic Rearrangements: Cope and Claisen Rearrangements.- 6.6. [2,3]-Sigmatropic Rearrangements.- 6.7. Ene Reactions.- 6.8. Unimolecular Thermal Elimination Reactions.- 6.8.1. Cheletropic Elimination.- 6.8.2. Decomposition of Cyclic Azo Compounds.- 6.8.3. ?-Eliminations Involving Cyclic Transition States.- General References.- Problems.- 7. Organometallic Compounds of Group I and II Metals.- 7.1. Preparation and Properties of Organolithium and Organomagnesium Compounds.- 7.2. Reactions of Organolithium and Organomagnesium Compounds.- 7.2.1. Reactions with Alkylating Agents.- 7.2.2. Reactions with Carbonyl Compounds.- 7.3. Organic Derivatives of Group IIB Metals.- 7.3.1. Organozinc Compounds.- 7.3.2. Organocadmium Compounds.- 7.3.3. Organomercury Compounds.- 7.4. Organocerium Compounds.- General References.- Problems.- 8. Reactions Involving the Transition Metals.- 8.1. Reactions Involving Organocopper Intermediates.- 8.2. Reactions Involving Organopalladium Intermediates.- 8.3. Reactions Involving Organonickel Compounds.- 8.4. Reactions Involving Rhodium, Iron, and Cobalt.- 8.5. Organometallic Compounds with v Bonding.- General References.- Problems.- 9. Carbon-Carbon Bond-Forming Reactions of Compounds of Boron, Silicon, and Tin.- 9.1. Organoboron Compounds.- 9.1.1. Synthesis of Organoboranes.- 9.1.2. Carbon-Carbon Bond-Forming Reactions.- 9.2. Organosilicon Compounds.- 9.2.1. Synthesis of Organosilanes.- 9.2.2. Carbon-Carbon Bond-Forming Reactions.- 9.3. Organotin Compounds.- 9.3.1. Synthesis of Organostannanes.- 9.3.2. Carbon-Carbon Bond-Forming Reactions.- General References.- Problems.- 10. Reactions Involving Highly Reactive Electron-Deficient Intermediates.- 10.1. Reactions Involving Carbocation Intermediates.- 10.1.1. Carbon-Carbon Bond-Formation Involving Carbocations.- 10.1.2. Rearrangements of Carbocations.- 10.1.3. Related Rearrangements.- 10.1.4. Fragmentation Reactions.- 10.2. Reactions Involving Carbenes and Nitrenes.- 10.2.1. Structure and Reactivity of Carbenes.- 10.2.2. Generation of Carbenes.- 10.2.3. Addition Reactions.- 10.2.4. Insertion Reactions.- 10.2.5. Rearrangement Reactions.- 10.2.6. Related Reactions.- 10.2.7. Nitrenes and Related Intermediates.- 10.2.8. Rearrangements to Electron-Deficient Nitrogen.- 10.3. Reactions Involving Free-Radical Intermediates.- 10.3.1. Sources of Radical Intermediates.- 10.3.2. Introduction of Functionality by Radical Reactions.- 10.3.3. Addition Reactions of Radicals with Substituted Alkenes.- 10.3.4. Cycl…