Page 21 - Advanced Organic Chemistry Part B - Reactions & Synthesis

Contents

Preface.................................................................. v

Acknowledgment and Personal Statement ................................ ix

Introduction ............................................................ xi

Chapter 1. Alkylation of Enolates and Other Carbon Nucleophiles ...... 1

Introduction........................................................................................................... 1
1.1. Generation and Properties of Enolates and Other Stabilized Carbanions... 2
1.1.1. Generation of Enolates by Deprotonation ........................................ 2
1.1.2. Regioselectivity and Stereoselectivity in Enolate Formation
from Ketones and Esters ................................................................... 5
1.1.3. Other Means of Generating Enolates................................................ 14
1.1.4. Solvent Effects on Enolate Structure and Reactivity ....................... 17
1.2. Alkylation of Enolates.................................................................................. 21
1.2.1. Alkylation of Highly Stabilized Enolates......................................... 21
1.2.2. Alkylation of Ketone Enolates.......................................................... 24
1.2.3. Alkylation of Aldehydes, Esters, Carboxylic Acids, Amides,
and Nitriles ........................................................................................ 31
1.2.4. Generation and Alkylation of Dianions............................................ 36
1.2.5. Intramolecular Alkylation of Enolates.............................................. 36
1.2.6. Control of Enantioselectivity in Alkylation Reactions..................... 41
1.3. The Nitrogen Analogs of Enols and Enolates: Enamines
and Imine Anions ......................................................................................... 46
General References............................................................................................... 55
Problems ............................................................................................................... 56
xxiii