Page 27 - Advanced Organic Chemistry Part B - Reactions & Synthesis

10.2. Reactions Involving Carbenes and Related Intermediates .......................... 903 xxix
10.2.1. Reactivity of Carbenes .................................................................... 905
Contents
10.2.2. Generation of Carbenes................................................................... 909
10.2.3. Addition Reactions.......................................................................... 916
10.2.4. Insertion Reactions.......................................................................... 934
10.2.5. Generation and Reactions of Ylides
by Carbenoid Decomposition.......................................................... 938
10.2.6. Rearrangement Reactions................................................................ 940
10.2.7. Related Reactions............................................................................ 941
10.2.8. Nitrenes and Related Intermediates ................................................ 944
10.2.9. Rearrangements to Electron-Deficient Nitrogen ............................ 947
10.3. Reactions Involving Free Radical Intermediates ......................................... 956
10.3.1. Sources of Radical Intermediates.................................................... 957
10.3.2. Addition Reactions of Radicals with Substituted Alkenes............. 959
10.3.3. Cyclization of Free Radical Intermediates ..................................... 967
10.3.4. Additions to C=N Double Bonds................................................... 973
10.3.5. Tandem Radical Cyclizations and Alkylations............................... 979
10.3.6. Fragmentation and Rearrangement Reactions ................................ 984
10.3.7. Intramolecular Functionalization by Radical Reactions................. 989
Problems ................................................................................................................. 992

Chapter 11. Aromatic Substitution Reactions ............................ 1003

Introduction............................................................................................................. 1003
11.1. Electrophilic Aromatic Substitution............................................................. 1004
11.1.1. Nitration........................................................................................... 1004
11.1.2. Halogenation.................................................................................... 1008
11.1.3. Friedel-Crafts Alkylation................................................................. 1014
11.1.4. Friedel-Crafts Acylation.................................................................. 1017
11.1.5. Related Alkylation and Acylation Reactions.................................. 1023
11.1.6. Electrophilic Metallation................................................................. 1026
11.2. Nucleophilic Aromatic Substitution............................................................. 1027
11.2.1. Aryl Diazonium Ions as Synthetic Intermediates........................... 1027
11.2.2. Substitution by the Addition-Elimination Mechanism................... 1035
11.2.3. Substitution by the Elimination-Addition Mechanism................... 1039
11.3. Transition Metal–Catalyzed Aromatic Substitution Reactions.................... 1042
11.3.1. Copper-Catalyzed Reactions ........................................................... 1042
11.3.2. Palladium-Catalyzed Reactions....................................................... 1045
11.4. Aromatic Substitution Reactions Involving Radical Intermediates............. 1052
11.4.1. Aromatic Radical Substitution ........................................................ 1052
11.4.2. Substitution by the S RN 1 Mechanism ............................................. 1053
Problems ................................................................................................................. 1056

Chapter 12. Oxidations.................................................. 1063

Introduction............................................................................................................. 1063
12.1. Oxidation of Alcohols to Aldehydes, Ketones, or Carboxylic Acids......... 1063
12.1.1. Transition Metal Oxidants............................................................... 1063
12.1.2. Other Oxidants................................................................................. 1070