Page 18 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

xviii 7.5. Intramolecular Catalysis of Carbonyl Substitution Reactions ...................... 668
7.6. Addition of Organometallic Reagents to Carbonyl Groups.......................... 676
Contents
7.6.1. Kinetics of Organometallic Addition Reactions................................ 677
7.6.2. Stereoselectivity of Organometallic Addition Reactions................... 680
7.7. Addition of Enolates and Enols to Carbonyl Compounds: The Aldol
Addition and Condensation Reactions .......................................................... 682
7.7.1. The General Mechanisms................................................................... 682
7.7.2. Mixed Aldol Condensations with Aromatic Aldehydes.................... 685
7.7.3. Control of Regiochemistry and Stereochemistry of Aldol
Reactions of Ketones.......................................................................... 687
7.7.4. Aldol Reactions of Other Carbonyl Compounds............................... 692
General References................................................................................................. 698
Problems ................................................................................................................. 698

Chapter 8. Aromaticity ................................................ 713

Introduction ............................................................................................................ 713
8.1. Criteria of Aromaticity................................................................................... 715
8.1.1. The Energy Criterion for Aromaticity................................................ 715
8.1.2. Structural Criteria for Aromaticity..................................................... 718
8.1.3. Electronic Criteria for Aromaticity .................................................... 720
8.1.4. Relationship among the Energetic, Structural, and Electronic
Criteria of Aromaticity ....................................................................... 724
8.2. The Annulenes ............................................................................................... 725
8.2.1. Cyclobutadiene.................................................................................... 725
8.2.2. Benzene............................................................................................... 727
8.2.3. 1,3,5,7-Cyclooctatetraene ................................................................... 727
8.2.4. [10]Annulenes—1,3,5,7,9-Cyclodecapentaene Isomers..................... 728
8.2.5. [12], [14], and [16]Annulenes ............................................................ 730
8.2.6. [18]Annulene and Larger Annulenes ................................................. 733
8.2.7. Other Related Structures..................................................................... 735
8.3. Aromaticity in Charged Rings....................................................................... 738
8.4. Homoaromaticity............................................................................................ 743
8.5. Fused-Ring Systems....................................................................................... 745
8.6. Heteroaromatic Systems ................................................................................ 758
General References ................................................................................................ 760
Problems................................................................................................................. 760

Chapter 9. Aromatic Substitution ...................................... 771

Introduction ............................................................................................................ 771
9.1. Electrophilic Aromatic Substitution Reactions ............................................. 771
9.2. Structure-Reactivity Relationships for Substituted Benzenes....................... 779
9.2.1. Substituent Effects on Reactivity ....................................................... 779
9.2.2. Mechanistic Interpretation of the Relationship between
Reactivity and Selectivity................................................................... 787
9.3. Reactivity of Polycyclic and Heteroaromatic Compounds........................... 791