Contents

Cover

Title Page

Copyright

Preface

Common Abbreviations

Biographical Statement

Part I: Introduction

Chapter 1: Localized Chemical Bonding

1.A. Covalent Bonding2

1.B. Multiple Valence

1.C. Hybridization

1.D. Multiple Bonds

1.E. Photoelectron Spectroscopy

1.F. Electronic Structures of Molecules

1.G. Electronegativity

1.H. Dipole Moment

1.I. Inductive and Field Effects

1.J. Bond Distances55

1.K. Bond Angles

1.L Bond Energies95

Chapter 2: Delocalized Chemical Bonding

2.A. Molecular Orbitals

2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds

2.C. Molecules that have Delocalized Bonds

2.D. Cross-Conjugation51

2.E. The Rules of Resonance

2.F. The Resonance Effect

2.G. Steric Inhibition of Resonance and the Influences of Strain

2.H. Pπ–dπ Bonding. Ylids

2.I. Aromaticity98

2.J. Alternant and Nonalternant Hydrocarbons208

2.K. Aromatic Systems with Electron Numbers Other than Six

2.L. Other Aromatic Compounds

2.M. Hyperconjugation

2.N. Tautomerism431

Chapter 3: Bonding Weaker Than Covalent

3.A. Hydrogen Bonding2

3.B. π–π Interactions

3.C. Addition Compounds

3.D. Catenanes and Rotaxanes190

3.E. Cucurbit[n]uril-Based Gyroscane

Chapter 4: Stereochemistry and Conformation

4.A. Optical Activity and Chirality3

4.B. What Kinds of Molecules Display Optical Activity?

4.C. The Fischer Projection

4.D. Absolute Configuration

4.E. The Cause of Optical Activity

4.F. Molecules with more than One Stereogenic Center

4.G. Asymmetric Synthesis

4.H. Methods of Resolution160

4.I. Optical Purity207

4.J. cistrans Isomerism

4.K. Out–In Isomerism

4.L. Enantiotopic and Diastereotopic Atoms, Groups, and Faces259

4.M. Stereospecific and Stereoselective Syntheses

4.N. Conformational Analysis

4.O. Molecular Mechanics412

4.P. Strain

Chapter 5: Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes

5.A. Carbocations2

5.B. Carbanions

5.C. Free Radicals

5.D. Carbenes

5.E. Nitrenes

Chapter 6: Mechanisms and Methods of Determining Them

6.A. Types of Mechanism

6.B. Types of Reaction

6.C. Thermodynamic Requirements For Reaction

6.D. Kinetic Requirements For Reaction

6.E. The Baldwin Rules For Ring Closure17

6.F. Kinetic and Thermodynamic Control

6.G. The Hammond Postulate

6.H. Microscopic Reversibility

6.I. Marcus Theory

6.J. Methods of Determining Mechanisms33

Chapter 7: Irradiation Processes in Organic Chemistry

7.A. Photochemistry3

7.B. Sonochemistry

7.C. Microwave Chemistry

Chapter 8: Acids and Bases

8.A. Brønsted Theory

8.B. The Mechanism of Proton-Transfer Reactions

8.C. Measurements of Solvent Acidity124

8.D. Acid and Base Catalysis148

8.E. Lewis Acids and Bases

8.F. The Effects of Structure on the Strengths of Acids and Bases175

8.G. The Effects of the Medium on Acid and Base Strength

Chapter 9: Effects of Structure and Medium on Reactivity

9.A. Resonance and Field Effects

9.B. Steric Effects

9.C. Quantitative Treatments of the Effect of Structure on Reactivity16

9.D. Effect of Medium on Reactivity and Rate

Part II: Introduction

Chapter 10: Aliphatic Substitution, Nucleophilic and Organometallic

10.A. Mechanisms

10.B. SET Mechanisms

10.C. The Neighboring-Group Mechanism113

10.D. The SNI Mechanism

10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements

10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism

10.G. Reactivity

10.H. Reactions

Chapter 11: Aromatic Substitution, Electrophilic

11.A. Mechanisms

11.B. Orientation and Reactivity

11.C. Quantitative Treatments of Reactivity in the Substrate

11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship

11.E. The Effect of the Leaving Group

11.F. Reactions

Chapter 12: Aliphatic, Alkenyl, and Alkynyl Substitution, Electrophilic and Organometallic

12.A. Mechanisms

12.B. Reactivity

12.C. Reactions

Chapter 13: Aromatic Substitution: Nucleophilic and Organometallic

13.A. Mechanisms

13.B. Reactivity

13.C. Reactions

Chapter 14: Substitution Reactions: Radical

14.A. Mechanisms

14.B. Reactivity

14.C. Reactions

Chapter 15: Addition to Carbon–Carbon Multiple Bonds

15.A. Mechanisms

15.B. Orientation and Reactivity

15.C. Reactions

Chapter 16: Addition to Carbon–Hetero Multiple Bonds

16.A. Mechanism and Reactivity

16.B. Reactions

Chapter 17: Eliminations

17.A. Mechanisms And Orientation

17.B. Regiochemistry of the Double Bond

17.C. Stereochemistry of the Double Bond

17.D. Reactivity

17.E. Mechanisms and Orientation in Pyrolytic Eliminations

17.F. Reactions

Chapter 18: Rearrangements

18.A. Mechanisms

18.B. Longer Nucleophilic Rearrangements

18.C. Free Radical Rearrangements54

18.D. Carbene Rearrangements86

18.E. Electrophilic Rearrangements94

18.F. Reactions

Chapter 19: Oxidations and Reductions

19.A. Mechanisms

19.B. Reactions

Appendix A: The Literature of Organic Chemistry

Appendix B: Classification of Reactions by Type of Compounds Synthesized

Indexes

Author Index

Subject Index