Page 28 - Advanced Organic Chemistry Part B - Reactions & Synthesis

xxx 12.2. Addition of Oxygen at Carbon-Carbon Double Bonds............................... 1074
12.2.1. Transition Metal Oxidants............................................................... 1074
Contents
12.2.2. Epoxides from Alkenes and Peroxidic Reagents............................ 1091
12.2.3. Subsequent Transformations of Epoxides ...................................... 1104
12.3. Allylic Oxidation .......................................................................................... 1116
12.3.1. Transition Metal Oxidants............................................................... 1116
12.3.2. Reaction of Alkenes with Singlet Oxygen ..................................... 1117
12.3.3. Other Oxidants................................................................................. 1124
12.4. Oxidative Cleavage of Carbon-Carbon Double Bonds ............................... 1126
12.4.1. Transition Metal Oxidants............................................................... 1126
12.4.2. Ozonolysis ....................................................................................... 1129
12.5. Oxidation of Ketones and Aldehydes .......................................................... 1131
12.5.1. Transition Metal Oxidants............................................................... 1131
12.5.2. Oxidation of Ketones and Aldehydes by Oxygen
and Peroxidic Compounds .............................................................. 1134
12.5.3. Oxidation with Other Reagents....................................................... 1143
12.6. Selective Oxidative Cleavages at Functional Groups.................................. 1144
12.6.1. Cleavage of Glycols ........................................................................ 1144
12.6.2. Oxidative Decarboxylation.............................................................. 1145
12.7. Oxidations at Unfunctionalized Carbon....................................................... 1148
Problems ................................................................................................................. 1151

Chapter 13. Multistep Syntheses......................................... 1163

Introduction............................................................................................................. 1163
13.1. Synthetic Analysis and Planning.................................................................. 1164
13.1.1. Retrosynthetic Analysis................................................................... 1164
13.1.2. Synthetic Equivalent Groups........................................................... 1166
13.1.3. Control of Stereochemistry ............................................................. 1171
13.2. Illustrative Syntheses.................................................................................... 1173
13.2.1. Juvabione......................................................................................... 1174
13.2.2. Longifolene...................................................................................... 1186
13.2.3. Prelog-Djerassi Lactone .................................................................. 1196
13.2.4. Baccatin III and Taxol .................................................................... 1210
13.2.5. Epothilone A.................................................................................... 1220
13.2.6. Discodermolide................................................................................ 1231
13.3. Solid Phase Synthesis................................................................................... 1245
13.3.1. Solid Phase Polypeptide Synthesis ................................................. 1245
13.3.2. Solid Phase Synthesis of Oligonucleotides..................................... 1250
13.4. Combinatorial Synthesis............................................................................... 1252
General References................................................................................................. 1259
Problems ................................................................................................................. 1260

References .............................................................. 1271

Index ................................................................... 1297