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PREFACE xiii COMMON ABBREVIATIONS xxi BIOGRAPHICAL STATEMENT xxv PART I INTRODUCTION 1 1. Localized Chemical Bonding 3 1.A. Covalent Bonding 3 1.B. Multiple Valence 6 1.C. Hybridization 7 1.D. Multiple Bonds 9 1.E. Photoelectron Spectroscopy 11 1.F. Electronic Structures of Molecules 14 1.G. Electronegativity 15 1.H. Dipole Moment 18 1.I. Inductive and Field Effects 19 1.J. Bond Distances 21 1.K. Bond Angles 25 1.L. Bond Energies 27 2. Delocalized Chemical Bonding 31 2.A. Molecular Orbitals 32 2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds 35 2.C. Molecules that have Delocalized Bonds 37 2.D. Cross–Conjugation 42 2.E. The Rules of Resonance 43 2.F. The Resonance Effect 45 2.G. Steric Inhibition of Resonance and the Influences of Strain 46 2.H. pp–dp Bonding. Ylids 49 2.I. Aromaticity 50 2.J. Alternant and Nonalternant Hydrocarbons 63 2.K. Aromatic Systems with Electron Numbers other than Six 65 2.L. Other Aromatic Compounds 82 2.M. Hyperconjugation 85 2.N. Tautomerism 89 3. Bonding Weaker Than Covalent 96 3.A. Hydrogen Bonding 96 3.B. p–p Interactions 103 3.C. Addition Compounds 104 3.D. Catenanes and Rotaxanes 118 3.E. Cucurbit[n]Uril–Based Gyroscane 121 4. Stereochemistry and Conformation 122 4.A. Optical Activity and Chirality 122 4.B. What Kinds of Molecules Display Optical Activity? 125 4.C. The Fischer Projection 136 4.D. Absolute Configuration 137 4.E. The Cause of Optical Activity 145 4.F. Molecules with more than One Stereogenic Center 146 4.G. Asymmetric Synthesis 149 4.H. Methods of Resolution 154 4.I. Optical Purity 160 4.J. cis???trans Isomerism 162 4.K. Out–In Isomerism 168 4.L. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 170 4.M. Stereospecific and Stereoselective Syntheses 173 4.N. Conformational Analysis 173 4.O. Molecular Mechanics 190 4.P. STRAIN 192 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 208 5.A. Carbocations 208 5.B. Carbanions 221 5.C. Free Radicals 234 5.D. Carbenes 249 5.E. Nitrenes 257 6. Mechanisms and Methods of Determining them 261 6.A. Types of Mechanism 261 6.B. Types of Reaction 262 6.C. Thermodynamic Requirements for Reaction 264 6.D. Kinetic Requirements for Reaction 266 6.E. The Baldwin Rules for Ring Closure 270 6.F. Kinetic and Thermodynamic Control 271 6.G. The Hammond Postulate 272 6.H. Microscopic Reversibility 273 6.I. Marcus Theory 273 6.J. Methods of Determining Mechanisms 275 7. Irradiation Processes in Organic Chemistry 289 7.A. Photochemistry 289 7.B. Sonochemistry 307 7.C. Microwave Chemistry 309 8. Acids and Bases 312 8.A. Brønsted Theory 312 8.B. The Mechanism of Proton–Transfer Reactions 323 8.C. Measurements of Solvent Acidity 324 8.D. Acid and Base Catalysis 327 8.E. Lewis Acids and Bases 330 8.F. The Effects of Structure on the Strengths of Acids and Bases 334 8.G. The Effects of the Medium on Acid and Base Strength 343 9. Effects of Structure and Medium on Reactivity 347 9.A. Resonance and Field Effects 347 9.B. Steric Effects 349 9.C. Quantitative Treatments of the Effect of Structure on Reactivity 352 9.D. Effect of Medium on Reactivity and Rate 361 PART II INTRODUCTION 367 10. Aliphatic Substitution, Nucleophilic and Organometallic 373 10.A. Mechanisms 373 10.B. SET Mechanisms 389 10.C. The Neighboring–Group Mechanism 391 10.D. The SNi Mechanism 408 10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 409 10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 413 10.G. Reactivity 417 10.H. Reactions 451 11. Aromatic Substitution, Electrophilic 569 11.A. Mechanisms 569 11.B. Orientation and Reactivity 576 11.C. Quantitative Treatments of Reactivity in the Substrate 586 11.D.A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 588 11.E. The Effect of the Leaving Group 591 11.F. Reactions 591 12. Aliphatic, Alkenyl, and Alkynyl Substitution, Electrophilic and Organometallic 649 12.A. Mechanisms 650 12.B. Reactivity 658 12.C. Reactions 660 13. Aromatic Substitution: Nucleophilic and Organometallic 732 13.A. Mechanisms 732 13.B. Reactivity 741 13.C. Reactions 745 14. Substitution Reactions: Radical 803 14.A. Mechanisms 803 14.B. Reactivity 812 14.C. Reactions 821 15. Addition to Carbon–Carbon Multiple Bonds 859 15.A. Mechanisms 859 15.B. Orientation and Reactivity 871 15.C. Reactions 881 16. Addition to Carbon–Hetero Multiple Bonds 1067 16.A. Mechanism and Reactivity 1067 16.B. Reactions 1075 17. Eliminations 1253 17.A. Mechanisms and Orientation 1253 17.B. Regiochemistry of the Double Bond 1269 17.C. Stereochemistry of the Double Bond 1273 17.D. Reactivity 1274 17.E. Mechanisms and Orientation in Pyrolytic Eliminations 1278 17.F. Reactions 1282 18. Rearrangements 1321 18.A. Mechanisms 1322 18.B. Longer Nucleophilic Rearrangements 1331 18.C. Free Radical Rearrangements 1333 18.D. Carbene Rearrangements 1337 18.E. Electrophilic Rearrangements 1337 18.F. Reactions 1337 19. Oxidations and Reductions 1433 19.A. Mechanisms 1434 19.B. Reactions 1436 APPENDIX A: THE LITERATURE OF ORGANIC CHEMISTRY 1569 APPENDIX B: CLASSIFICATION OF REACTIONS BY TYPE OF COMPOUNDS SYNTHESIZED 1605 INDEXES AUTHOR INDEX 1631 SUBJECT INDEX 1835