Contents Preface v Acknowledgment and Personal Statement vii Introduction ix Chapter 1 Chemical Bonding and Molecular Structure 1 Introduction ix1.1 Description of Molecular Structure Using Valence Bond Concepts 2 1 1.1 Hybridization 4 1.1.2 The Origin of Electron-Electron Repulsion 7 1.1.3 Electronegativity and Polarity 8 1.1.4 Electronegativity Equahzat10n 11 1.1.5 Differential Electronegativity of Carbon Atoms 12 1.1.6 Polarizability， Hardness， and Softness 14 1.1.7 Resonance and Conjugation 18 1.1.8 Hyperconjugation 22 1.1.9 Covalent and van der Waals Radii of Atoms 24 1.2 Molecular Orbital Theory and Methods 26 I 2.1 The Huckel MO Method 27 1.2.2 Semiempirical MO Methods 32 1.2.3 Ab Initio Methods 32 1.2.4 Pictorial Representation of MOs for Molecules 35 1.2.5 Qualitative Application of MO Theory to Reactivity: Perturbational MO Theory and Frontier Orbitals 41 1.2.6 Numerical Application of MO Theory 50 1.3 Electron Density Functionals 54 1.4 Representation of Electron Density Distribution 57 1.4 1 Mululliken Populat10n Analysis 60 1.4.2 Natural Bond Orbitals and Natural Population Analysis 61 1.4.3 Atoms m Molecules 63 1.4.4 Comparison and Interpretation of Atomic Charge Calculations 70 1.4.5 Electrostatic Potential Surfaces 73 1.4.6 Relationships between Electron Density and Bond Order 76 Topic 1.1 The Origin of the Rotational (Torsional) Barrier in Ethane and Other Small Molecules 78 Topic 1.2 Heteroatom Hyperconjugation (Anomeric Effect) in Acyclic Molecules 81 Topic 1.3 Bonding in Cyclopropane and Other Small Ring Compounds 85 Topic 1.4 Representation of Electron Density by the Laplacian Function 92 Topic 1.5 Application of Density Functional Theory to Chemical Properties and Reactivity 94 T.1.5.1 DFT Formulation of Chemical Potential， Electronegativity， Hardness and Softness， and Covalent and van der Waal Radii 95 T.1.5.2 DFT Formulation of Reactivity-The Fukui Function 97 T.1.5.3 DFT Concepts of Substituent Groups Effects 100 General References 106 Problems 106 Chapter 2 Stereochemistry， Conformation， and Stereoselectivity 119 Introduction 119 2.1 Configuration 119 2.1.1 Configuration at Double Bonds 119 2.1.2 Configuration of Cyclic Compounds 121 2.1.3 Configuration at Tetrahedral Atoms 122 2.1.4 Molecules with Multiple Stereogenic Centers 126 2.1.5 Other Types of Stereogenic Centers 128 2.1.6 The Relationship between Chirality and Symmetry 131 2.1 7 Configuration at Prochiral Centers 133 2.1.8 Resolution—The Separation of Enantiomers 136 2.2 Conformation 142 2.2 l Conformation of Acyclic Compounds 142 2.2.2 Conformations of Cyclohexane Derivatives 152 2.2.3 Conformations of Carbocyclic Rings of Other Sizes 161 2.3 Molecular Mechanics 167 2.4 Stereoselective and Stereospecific Reactions 169 2.4.1 Examples of Stereoselective Reactions 170 2.4.2 Examples of Stereospecific Reactions 182 2.5 Enantioselective React10ns 189 2.5.1 Enantioselective Hydrogenation 189 2.5.2 Enantioselective Reduction of Ketones 193 2.5.3 Enantioselective Epoxidation of Allylic Alcohols 196 2.5.4 Enantioselective Dihydroxylation of Alkenes 200 2.6 Double Stereodifferentiation: Reinforcing and Competing Stereoselect1v1ty 204 Topic 2.1 Analysis and Separation of Enantiomeric Mixtures 208 T.2.1.1 Chiral Shift Reagents and Chiral Solvating Agents 208 T.2.1.2 Separation of Enantiomers 211 Topic 2.2 Enzymatic Resolution and Desymmetrization 215 T.2.2.1 Li pases and Esterases 216 T.2.2.2 Proteases and Acy lases 222 T.2.2.3 Epoxide Hydrolases 224 Topic 2.3 The Anomeric Effect in Cyclic Compounds 227 Topic 2.4 Polar Substituent Effects in Reduction of Carbonyl Compounds 234 General References 239 Problems 240 Chapter 3 Structural Effects on Stability and Reactivity 253 Introduction 253 3.1 Thermodynamic Stability 254 3.1.1 Relationship between Structure and Thermodynamic Stability for Hydrocarbons 256 3.1.2 Calculation of Enthalpy of Formation and Enthalpy of Reaction 257 3.2 Chemical Kinetics 270 3.2.1 Fundamental Principles of Chemical Kinetics 270 3.2.2 Representation of Potential Energy Changes m Reacllons 273 3.2.3 Reaction Rate Expressions 280 3.2.4 Examples of Rate Expressions 283 3.3 General Relationships between Thermodynamic Stability and Reaction Rates 285 3.3.1 Kinetic versus Thermodynamic Control of Product Composition 285 3.3.2 Correlations between Thermodynamic and Kinetic Aspects of Reactions 287 3.3.3 Curtm-Hammett Prmciple 296 3.4 Electronic Substituent Effects on Reaction Intermediates 297 3 4.1 Carbocations 300 3.4.2 Carbanions 307 3.4 3 Radical Intermediates 311 3.4.4 Carbonyl Addition Intermediates 319 3.5 Kinetic Isotope Effects 33
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