Contents:

of Part A.- 1. Chemical Bonding and Molecular Structure.- 1.1. Valence-Bond Approach to Chemical Bonding.- 1.2. Bond Energies, Lengths, and Dipoles.- 1.3. Molecular Orbital Theory.- 1.4. Huckel Molecular Orbital Theory.- General References.- Problems.- 2. Stereochemical Principles.- 2.1. Enantiomeric Relationships.- 2.2. Diastereomeric Relationships.- 2.3. Dynamic Stereochemistry.- 2.4. Prochiral Relationships.- General References.- Problems.- 3. Conformational and Other Steric Effects.- 3.1. Steric Strain and Molecular Mechanics.- 3.2. Conformations of Acyclic Molecules.- 3.3. Conformations of Cyclohexane Derivatives.- 3.4. Carbocyclic Rings Other Than Six-Membered.- 3.5. Heterocyclic Conformational Analysis.- 3.6. Molecular Orbital Methods Applied to Conformational Analysis.- 3.7. Conformational Effects on Reactivity.- 3.8. Other Steric Effects on Reactivity.- General References.- Problems.- 4. Study and Description of Organic Reaction Mechanisms.- 4.1. Thermodynamic Data.- 4.2. Kinetic Data.- 4.3. Substituent Effects and Linear Free-Energy Relationships.- 4.4. Isotope Effects.- 4.5. Characterization of Reaction Intermediates.- 4.6. Catalysis.- 4.7. Solvent Effects.- 4.8. Basic Mechanistic Concepts: Kinetic Versus Thermodynamic Control, Hammond’s Postulate, the Curtin-Hammett Principle.- 4.9. Isotopes in Labeling Experiments.- 4.10. Stereochemistry.- General References.- Problems.- 5. Nucleophilic Substitution.- 5.1. The Limiting Cases—Substitution by the Ionization (Sn1) Mechanism.- 5.2. The Limiting Cases—Substitution by the Direct Displacement (SN2) Mechanism.- 5.3. Alternative Mechanistic Hypotheses.- 5.4. Carbonium Ions.- 5.5. Nucleophilicity.- 5.6. Leaving-Group Effects.- 5.7. Steric and Other Substituent Effects on Substitution and Ionization Rates.- 5.8. Stereochemistry of Nucleophilic Substitution.- 5.9. Secondary Kinetic Isotope Effects in Substitution Mechanisms.- 5.10. Neighboring-Group Participation.- 5.11. Carbonium Ion Rearrangements.- 5.12. Nonclassical Carbonium Ions and the Norbornyl Cation Problem.- 5.13. Synthetic Applications of Nucleophilic Substitution Reactions.- General References.- Problems.- 6. Polar Addition and Elimination Reactions.- 6.1. Addition of Hydrogen Halides to Alkenes.- 6.2. Acid-Catalyzed Hydration of Alkenes.- 6.3. Addition of Halogens.- 6.4. The E2, E1, and E1cb Mechanisms.- 6.5. Orientation Effects in Elimination Reactions.- 6.6. Stereochemistry of E2 Elimination Reactions.- 6.7. Dehydration of Alcohols.- 6.8. Eliminations Not Involving C-H Bonds.- General References.- Problems.- 7. Carbanions and Other Nucleophilic Carbon Species.- 7.1. Acidity of Hydrocarbons.- 7.2. Carbanions Stabilized by Functional Groups.- 7.3. Enols and Enamines.- General References.- Problems.- 8. Reactions of Carbonyl Compounds.- 8.1. Hydration and Addition of Alcohols to Aldehydes and Ketones.- 8.2. Addition-Elimination Reactions of Ketones and Aldehydes.- 8.3. Reactivity of Carbonyl Compounds toward Addition.- 8.4. Ester Hydrolysis and Related Reactions.- 8.5. Amide Hydrolysis.- 8.6. Acylation of Nucleophilic Oxygen and Nitrogen Groups.- 8.7. Intramolecular Catalysis.- General References.- Problems.- 9. Aromaticity and Electrophilic Aromatic Substitution.- 9.1. Aromaticity.- 9.1.1. The Concept of Aromaticity.- 9.1.2. The Annulenes.- 9.1.3. Aromaticity in Charged Rings.- 9.1.4. Fused-Ring Systems.- 9.1.5. Homoaromaticity.- 9.2. Electrophilic Aromatic Substitution Reactions.- 9.3. Structure-Reactivity Relationships.- 9.4. Specific Substitution Mechanisms.- 9.4.1. Nitration.- 9.4.2. Halogenation.- 9.4.3. Protonation and Hydrogen Exchange.- 9.4.4. Friedel-Crafts Alkylation and Related Reactions.- 9.4.5. Friedel-Crafts Acylation and Related Reactions.- 9.4.6. Coupling with Diazonium Compounds.- 9.4.7. Substitution of Groups Other Than Hydrogen.- 9.5. Theoretical Treatments of Aromatic Substitution Reactions.- General References.- Problems.- 10. Concerted Reactions.- 10.1. Electrocyclic Reactions.- 10.2. Sigmatropic Rearrangements.- 10.3. Cycloaddition and Cycloelimination Reactions.- General References.- Problems.- 11. Photochemistry.- 11.1. General Principles.- 11.2. Orbital Symmetry Considerations Related to Photochemical Reactions.- 11.3. Photochemistry of Carbonyl Groups.- 11.4. Photochemistry of Alkenes and Dienes.- 11.5. Photochemistry of Aromatic Compounds.- General References.- Problems.- 12. Free-Radical Reactions.- 12.1. Generation and Characterization of Free Radicals.- 12.1.1. Background.- 12.1.2. Stable Free Radicals.- 12.1.3. Direct Detection of Radical Intermediates.- 12.1.4. Sources of Free Radicals.- 12.1.5. Structural and Stereochemical Properties of Radical Intermediates.- 12.1.6. Charged Radical Species.- 12.2. Characteristics of Reaction Mechanisms Involving Radical Intermediates.- 12.2.1. Kinetic Characteristics of Chain Reactions.- 12.2.2. Structure-Reactivity Relationships.- 12.3. Free-Radical Substitution Reactions.- 12.3.1. Halogenation.- 12.3.2. Oxidation.- 12.3.3. Substitutions Involving Aryl Radicals.- 12.4. Free-Radical Addition Reactions.- 12.4.1. Addition of Hydrogen Halides.- 12.4.2. Addition of Halomethanes.- 12.4.3. Addition of Other Carbon Radicals.- 12.4.4. Addition of S-H Compounds.- 12.5. Intramolecular Free-Radical Reactions.- 12.6. Rearrangement and Fragmentation Reactions of Free Radicals.- 12.6.1. Rearrangement.- 12.6.2. Fragmentation.- 12.7. Electron-Transfer Reactions.- General References.- Problems.- References for Problems.