Advanced Organic Synthesis

PrefaceI. Functional Group Modifications 1. Chemical Oxidations I. Chromium Trioxide Oxidation II. Periodate—Permanganate Cleavage of Olefins III. Free Radical Oxidation of an Allylic Position IV. Epoxidation of Olefins V. Baeyer-Villiger Oxidation of Ketones VI. Lead Tetraacetate Oxidation of Cycloalkanols VII. Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime VIII. Oxidation of Ethers to Esters IX. Partial Oxidation of an Aliphatic Side Chain X. Bisdecarboxylation with Lead Tetraacetate XI. Oxidation with Selenium Dioxide References 2. Hydride and Related Reductions I. Reduction by Lithium Aluminum Hydride II. Mixed Hydride Reduction III. Reduction with Iridium-Containing Catalysts IV. Reduction of Conjugated Alkenes with Chromium (II) Sulfate References 3. Dissolving Metal Reductions I. Reduction by Lithium—Amine II. Reduction by Lithium—Ethylenediamine III. Reduction of α,β-Unsaturated Ketones by Lithium—Ammonia IV. Reduction of α,β-Unsaturated Ketones in Hexamethylphosphoric Triamide V. Reduction of an α,β-Unsaturated Υ-Diketone with Zinc References 4. Hydroboration I. Hydroboration of Olefins as a Route to Alcohols II. Selective Hydroborations Using Bis(3-Methyl-2-Butyl)Borane (BMB) III. Purification of a Mixture of Δ9,10- and Δ1(9)-Octalins References 5. Catalytic Hydrogenation I. Hydrogenation Over Platinum Catalyst II. Low-Pressure Hydrogenation of Phenols Over Rhodium Catalysts III. Cis-4-Hydroxycyclohexanecarboxylic Acid from p-Hydroxybenzoic Acid IV. 3-Isoquinuclidone from p-Aminobenzoic Acid V. Homogeneous Catalytic Hydrogenation References 6. The Introduction of Halogen I. Halides from Alcohols by Triphenylphosphine—Carbon Tetrahalide II. Halides from Alcohols and Phenols by Triphenylphosphine Dihalide III. Allylic and Benzylic Bromination with N-Bromosuccinimide IV. α-Bromination of Ketones and Dehydrobromination V. Stereospecific Synthesis of Trans-4-Halocyclohexanols References 7. Miscellaneous Elimination, Substitution, and Addition Reactions I. Methylenecyclohexane by Pyrolysis of an Amine Oxide II. The Wolff-Kishner Reduction III. Dehydration of 2-Decalol IV. Boron Trifluoride Catalyzed Hydrolysis of Nitriles V. Bridged Sulfides by Addition of Sulfur Dichloride to Dienes VI. Methylation by Diazomethane VII. Oxymercuration: A Convenient Route to Markovnikov Hydration of Olefins VIII. Esterification of Tertiary Alcohols IX. Ketalization X. Half-Esterification of a Diol XI. Substitution on Ferrocene XII. Demethylation of Aryl Methyl Ethers by Boron Tribromide ReferencesII. Skeletal Modifications 8. The Diels-Alder Reaction I. 3,6-Diphenyl-4,5-Cyclohexenedicarboxylic Anhydride II. Reactions with Butadiene III. Catalysis by Aluminum Chloride IV. Generation of Dienes from Diones V. Reactions with Cyclopentadiene References 9. Enamines as Intermediates I. Preparation of the Morpholine Enamine of Cyclohexanone II. Acylation of Enamines III. Enamines as Michael Addition Reagents IV. Reactions of Enamines with β-Propiolactone V. Reactions of Enamines with Acrolein References 10. Enolate Ions as Intermediates I. Ketones as Enolates: Carbethoxylation of Cyclic Ketones II. Esters as Enolates: 1,4-Cyclohexanedione and Meerwein's Ester III. Methylsulfinyl Carbanion as a Route to Methyl Ketones IV. Cyclization with Diethyl Malonate V. Carboxylations with Magnesium Methyl Carbonate (MMC) VI. Alkylationof β-Ketoesters VII. The Robinson Annelation Reaction References 11. The Wittig Reaction I. Benzyl-Containing Ylides II. Alkyl Ylides Requiring n-Butyl Lithium III. Methylsulfinyl Carbanion in the Generation of Ylides IV. The Wittig Reaction Catalyzed by Ethylene Oxide V. Cyclopropylidene Derivatives via the Wittig Reaction References 12. Reactions of Trialkylboranes I. Trialkylcarbinols from Trialkylboranes and Carbon Monoxide II. Dialkylketones from Trialkylboranes and Carbon Monoxide—Water III. The Reaction of Trialkylboranes with Methyl Vinyl Ketone and Acrolein IV. The Reaction of Trialkylboranes with Ethyl Bromoacetate References 13. Carbenes as Intermediates I. Carbene Addition by the Zinc-Copper Couple II. Dibromocarbenes III. Dihalocarbenes from Phenyl(trihalomethyl)mercury Compounds References 14. Ethynylation I. Generation of Sodium Acetylide in Liquid Ammonia II. The Generation of Sodium Acetylide in Tetrahydrofuran III. The Generation of Sodium Acetylide Via Dimsylsodium References 15. Structural Isomerizations I. Acid Catalyzed Rearrangement of Saturated Hydrocarbons II. Photolytic Ring Contraction III. Isomerization of 1-Ethynylcylohexanol: Three Methods IV. Photolytic Isomerization of 1,5-Cyclooctadiene V. Oxidative Rearrangement of β-Diketones VI. Base Catalyzed Rearrangement of 4-Benzoyloxycyclohexanone VII. Allenes from 1,1-Dihalocyclopropanes by Methyllithium References 16. Elimination, Substitution, and Addition Reactions Resulting in Carbon—Carbon Bond Formation I. Carboxylation of Carbonium Ions II. Paracyclophane via a 1,6-Hofmann Elimination III. Diphenylcyclopropenone from Commercial Dibenzyl Ketone IV. Phenylcyclopropane from Cinnamaldehyde V. Conversion of Alkyl Chlorides to Nitriles in DMSO VI. Photolytic Addition of Formamide to Olefins VII. Intermolecular Dehydrohalogenation VIII. Ring Enlargement with Diazomethane IX. Conjugate Addition of Grignard Reagents X. Dimethyloxosulfonium Methylide in Methylene Insertions XI. Acylation of a Cycloalkane: Remote Functionalization XII. The Modified Hunsdiecker Reaction References 17. Miscellaneous Preparations I. Derivatives of Adamantane II. Percarboxylic Acids III. Diazomethane IV. Trichloroisocyanuric Acid ReferencesAppendix 1. Examples of Multistep SynthesesAppendix 2. Sources of Organic ReagentsAppendix 3. Introduction to the Techniques of Synthesis I. The Reaction II. The Workup III. Purification of the Product ReferencesSubject Index