Table of Contents

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. pπ–dπ 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. π–π 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

About the Author

MICHAEL B. SMITH, PhD, is Professor in the Department of Chemistry at the University of Connecticut. He is a coauthor of the fifth and sixth editions of March's Advanced Organic Chemistry and the author of Volumes 6 - 12 of the Compendium of Organic Synthetic Methods (Wiley) as well as several other monographs.

Reviews

"In conclusion, this latest, mammoth edition of March/Smith ishighly recommended." (Organic Process Research &Development, 1 June 2013)