Page 22 - Advanced Organic Chemistry Part B - Reactions & Synthesis

xxiv Chapter 2. Reactions of Carbon Nucleophiles
with Carbonyl Compounds ................................. 63
Contents
Introduction........................................................................................................... 63
2.1. Aldol Addition and Condensation Reactions............................................... 64
2.1.1. The General Mechanism ................................................................... 64
2.1.2. Control of Regio- and Stereoselectivity of Aldol Reactions
of Aldehydes and Ketones ................................................................ 65
2.1.3. Aldol Addition Reactions of Enolates of Esters
and Other Carbonyl Derivatives ....................................................... 78
2.1.4. The Mukaiyama Aldol Reaction....................................................... 82
2.1.5. Control of Facial Selectivity in Aldol and Mukaiyama Aldol
Reactions............................................................................................ 86
2.1.6. Intramolecular Aldol Reactions and the Robinson Annulation ....... 134
2.2. Addition Reactions of Imines and Iminium Ions ........................................ 139
2.2.1. The Mannich Reaction ...................................................................... 140
2.2.2. Additions to N-Acyl Iminium Ions................................................... 145
2.2.3. Amine-Catalyzed Condensation Reactions....................................... 147
2.3. Acylation of Carbon Nucleophiles............................................................... 148
2.3.1. Claisen and Dieckmann Condensation Reactions ............................ 149
2.3.2. Acylation of Enolates and Other Carbon Nucleophiles ................... 150
2.4. Olefination Reactions of Stabilized Carbon Nucleophiles.......................... 157
2.4.1. The Wittig and Related Reactions of Phosphorus-Stabilized
Carbon Nucleophiles ......................................................................... 157
2.4.2. Reactions of -Trimethylsilylcarbanions with Carbonyl
Compounds........................................................................................ 171
2.4.3. The Julia Olefination Reaction ......................................................... 174
2.5. Reactions Proceeding by Addition-Cyclization........................................... 177
2.5.1. Sulfur Ylides and Related Nucleophiles........................................... 177
2.5.2. Nucleophilic Addition-Cyclization of -Haloesters......................... 182
2.6. Conjugate Addition by Carbon Nucleophiles.............................................. 183
2.6.1. Conjugate Addition of Enolates........................................................ 183
2.6.2. Conjugate Addition with Tandem Alkylation .................................. 189
2.6.3. Conjugate Addition by Enolate Equivalents..................................... 190
2.6.4. Control of Facial Selectivity in Conjugate
Addition Reactions............................................................................ 193
2.6.5. Conjugate Addition of Organometallic Reagents............................. 197
2.6.6. Conjugate Addition of Cyanide Ion.................................................. 198
General References............................................................................................... 200
Problems ............................................................................................................... 200

Chapter 3. Functional Group Interconversion
by Substitution, Including Protection and Deprotection ...... 215

Introduction........................................................................................................... 215
3.1. Conversion of Alcohols to Alkylating Agents............................................. 216
3.1.1. Sulfonate Esters................................................................................. 216
3.1.2. Halides............................................................................................... 217