March's Advanced Organic Chemistry

MICHAEL B. SMITH, PHD, is Professor Emeritus in the Department of Chemistry at the University of Connecticut. He is a coauthor of the fifth through seventh editions of March's Advanced Organic Chemistry and the author of Volumes 6 - 13 of the Compendium of Organic Synthetic Methods, as well as several other monographs and textbooks.

New Reaction Sections Correlation: 7th Edition 8th Edition xv Preface xxi Common Abbreviations xxv Biographical Statement xxxi New Features of the 8th Edition xxxiii Part I Introduction 1 1. Localized Chemical Bonding 3 1.A. Covalent Bonding 3 1.B. Multiple Valence 7 1.C. Hybridization 7 1.D. Multiple Bonds 9 1.E. Photoelectron Spectroscopy 12 1.F. Electronic Structures of Molecules 15 1.G. Electronegativity 17 1.H. Dipole Moment 19 1.I. Inductive and Field Effects 20 1.J. Bond Distances 23 1.K. Bond Angles 27 1.L. Bond Energies 29 2. Delocalized Chemical Bonding 33 2.A. Molecular Orbitals 34 2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds 37 2.C. Molecules that have Delocalized Bonds 39 2.D. Cross Conjugation 44 2.E. The Rules of Resonance 46 2.F. The Resonance Effect 48 2.G. Steric Inhibition of Resonance and the Influences of Strain 48 2.H. pd Bonding: Ylids 52 2.I. Aromaticity 54 2.I.i. Six-Membered Rings 58 2.I.ii. Five-, Seven-, and Eight-Membered Rings 62 2.I.iii. Other Systems Containing Aromatic Sextets 67 2.J. Alternant and Nonalternant Hydrocarbons 68 2.K. Aromatic Systems with Electron Numbers Other Than Six 70 2.K.i. Systems of Two Electrons 72 2.K.ii. Systems of Four Electrons: Antiaromaticity 73 2.K.iii. Systems of Eight Electrons 76 2.K.iv. Systems of Ten Electrons 77 2.K.v. Systems of More than Ten Electrons: 4n + 2 Electrons 80 2.K.vi. Systems of More Than Ten Electrons: 4n Electrons 85 2.L. Other Aromatic Compounds 89 2.M. Hyperconjugation 92 2.N. Tautomerism 96 2.N.i. KetoEnol Tautomerism 97 2.N.ii. Other Proton-Shift Tautomerism 100 3. Bonding Weaker Than Covalent 105 3.A. Hydrogen Bonding 105 3.B. Interactions 113 3.C. Addition Compounds 114 3.C.i. Electron DonorAcceptor (EDA) Complexes 114 3.C.ii. Crown Ether Complexes and Cryptates 117 3.C.iii. Inclusion Compounds 122 3.C.iv. Cyclodextrins 125 3.D. Catenanes and Rotaxanes 127 3.E. Cucurbit[n]Uril-Based Gyroscane 131 4. Stereochemistry and Conformation 133 4.A. Optical Activity and Chirality 133 4.B. Dependence of Rotation on Conditions of Measurement 135 4.C. What Kinds of Molecules Display Optical Activity? 136 4.D. The Fischer Projection 147 4.E. Absolute Configuration 148 4.E.i. The Cahn-Ingold-Prelog System 150 4.E.ii. Methods of Determining Configuration 152 4.F. The Cause of Optical Activity 156 4.G. Molecules with More Than One Stereogenic Center 157 4.H. Asymmetric Synthesis 161 4.I. Methods of Resolution 166 4.J. Optical Purity 173 4.K. CisTrans Isomerism 175 4.K.i. CisTrans Isomerism Resulting from Double Bonds 175 4.K.ii. CisTrans Isomerism of Monocyclic Compounds 179 4.K.iii. CisTrans Isomerism of Fused and Bridged Ring Systems 180 4.L. OutIn Isomerism 181 4.M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 183 4.N. Stereospecific and Stereoselective Syntheses 186 4.O. Conformational Analysis 187 4.O.i. Conformation in Open-Chain Systems 188 4.O.ii. Conformation in Six-Membered Rings 194 4.O.iii. Conformation in Six-Membered Rings Containing Heteroatoms 199 4.O.iv. Conformation in Other Rings 202 4.P. Molecular Mechanics 204 4.Q. Strain 206 4.Q.i. Strain in Small Rings 207 4.Q.ii. Strain in Other Rings 213 4.Q.iii. Unsaturated Rings 215 4.Q.iv. Strain Due to Unavoidable Crowding 218 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 223 5.A. Carbocations 224 5.A.i. Nomenclature 224 5.A.ii. Stability and Structure of Carbocations 224 5.A.iii. The Generation and Fate of Carbocations 234 5.B. Carbanions 237 5.B.i. Stability and Structure 237 5.B.ii. The Structure of Organometallic Compounds 244 5.B.iii. The Generation and Fate of Carbanions 249 5.C. Free Radicals 250 5.C.i. Stability and Structure 250 5.C.ii. The Generation and Fate of Free Radicals 261 5.C.iii