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.
Reihe
Auflage
Sprache
Verlagsort
Verlagsgruppe
Illustrationen
3
3 s/w Abbildungen
LVI, 799 p. 3 illus.
ISBN-13
978-1-4613-9797-7 (9781461397977)
DOI
10.1007/978-1-4613-9797-7
Schweitzer Klassifikation
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.- 2.2. Condensation Reactions of Imines and Iminium Ions.- 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.- 3.2. Introduction of Functional Groups by Nucleophilic Substitution at Saturated Carbon.- 3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters.- 3.4. Interconversion of Carboxylic Acid Derivatives.- 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 andAlkynes.- 4.9. Addition at Double Bonds via Organoboranes.- General References.- Problems.- 5. Reduction of Carbonyl and Other Functional Groups.- 5.1. Addition of Hydrogen.- 5.2. Group III Hydride-Donor Reagents.- 5.3. Group IV Hydride Donors.- 5.4. Hydrogen Atom Donors.- 5.5. Dissolving-Metal Reductions.- 5.6. Reductive Deoxygenation of Carbonyl Groups.- General References.- Problems.- 6. Cycloadditions, Unimolecular Rearrangements, and Thermal Eliminations.- 6.1. Cycloaddition 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.- 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.- 7.3. Organic Derivatives of Group IIB Metals.- 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.- 9.2. Organosilicon Compounds.- 9.3. Organotin Compounds.- General References.- Problems.- 10. Reactions Involving Highly Reactive Electron-Deficient Intermediates.- 10.1. Reactions Involving Carbocation Intermediates.- 10.2. Reactions Involving Carbenes and Nitrenes.- 10.3. Reactions Involving Free-Radical Intermediates.- General References.- Problems.- 11. Aromatic Substitution Reactions.- 11.1. Electrophilic Aromatic Substitution.- 11.2. Nucleophilic Aromatic Substitution.- 11.3. Aromatic Radical Substitution Reactions.- 11.4. Substitution by the SRN1 Mechanism.- General References.- Problems.- 12. Oxidations.- 12.1. Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids.- 12.2. Addition of Oxygen at Carbon-Carbon Double Bonds.- 12.3. Cleavage of Carbon-Carbon Double Bonds.- 12.4. Selective Oxidative Cleavages at Other Functional Groups.- 12.5. Oxidation of Ketones and Aldehydes.- 12.6. Allylic Oxidation.- 12.7. Oxidations at Unfunctionalized Carbon.- General References.- Problems.- 13. Multistep Syntheses.- 13.1. Protective Groups.- 13.2. Synthetic Equivalent Groups.- 13.3. Synthetic Analysis and Planning.- 13.4. Control of Stereochemistry.- 13.5. Illustrative Syntheses.- General References.- Problems.- References for Problems.
