Pierre Vogel is Professor of organic chemistry at the EPFL in Lausanne, Switzerland. He has published three books and has co-authored more than 490 publications in the fields of physical organic chemistry, organic and organometallic synthesis, total asymmetric synthesis of natural products of biological interest, catalysis, glycochemistry and bio-organic chemistry.Kendall N. Houk is Saul Winstein Professor at the UCLA. He is an authority on theoretical and computational organic chemistry. His group develops rules to understand reactivity, computationally models complex organic reactions, and experimentally tests the predictions of theory. He collaborates prodigiously with chemists all over the world. He has published nearly 1100 articles in refereed journals and is among the 100 most-cited chemists.

• Organic Chemistry: Theory, Reactivity and Mechanisms in Modern SynthesisPreface xvForeword xxix1 Equilibria and thermochemistry 11.1 Introduction 11.2 Equilibrium-free enthalpy: reaction-free energy or Gibbs energy 11.3 Heat of reaction and variation of the entropy of reaction (reaction entropy) 21.4 Statistical thermodynamics 41.5 Standard heats of formation 81.6 What do standard heats of formation tell us about chemical bonding and ground-state properties of organic compounds? 91.7 Standard heats of typical organic reactions 141.8 Ionization energies and electron affinities 201.9 Homolytic bond dissociations; heats of formation of radicals 221.10 Heterolytic bond dissociation enthalpies 281.11 Electron transfer equilibria 321.12 Heats of formation of neutral, transient compounds 321.13 Electronegativity and absolute hardness 371.14 Chemical conversion and selectivity controlled by thermodynamics 401.15 Thermodynamic (equilibrium) isotopic effects 492 Additivity rules for thermodynamic parameters and deviations 1092.1 Introduction 1092.2 Molecular groups 1102.3 Determination of the standard group equivalents (group equivalents) 1112.4 Determination of standard entropy increments 1132.5 Steric effects 1142.6 Ring strain and conformational flexibility of cyclic compounds 1172.7 ;;/π-, n/π-, σ/π-, and n/σ-interactions 1272.8 Other deviations to additivity rules 1442.9 Major role of translational entropy on equilibria 1462.10 Entropy of cyclization: loss of degrees of free rotation 1512.11 Entropy as a synthetic tool 1513 Rates of chemical reactions 1773.1 Introduction 1773.2 Differential and integrated rate laws 1773.3 Activation parameters 1883.4 Relationship between activation entropy and the reaction mechanism 1923.5 Competition between cyclization and intermolecular condensation 1973.6 Effect of pressure: activation volume 2013.7 Asymmetric organic synthesis 2063.8 Chemo- and site-selective reactions 2293.9 Kinetic isotope effects and reaction mechanisms 2314 Molecular orbital theories 271.1 Introduction 2714.2 Background of quantum chemistry 2714.3 Schrödinger equation 2724.4 Coulson and Longuet-Higgins approach 2744.5 Hückel method 2774.6 Aromatic stabilization energy of heterocyclic compounds 3054.7 Homoconjugation 3084.8 Hyperconjugation 3144.9 Heilbronner Möbius aromatic [N]annulenes 3244.10 Conclusion 3265 Pericyclic reactions 3395.1 Introduction 3395.2 Electrocyclic reactions 3405.3 Cycloadditions and cycloreversions 3615.4 Cheletropic reactions 4375.5 Thermal sigmatropic rearrangements 4515.6 Dyotropic rearrangements and transfers 4955.7 Ene-reactions and related reactions 5006 Organic photochemistry 6156.1 Introduction 6156.2 Photophysical processes of organic compounds 6156.3 Unimolecular photochemical reactions of unsaturated hydrocarbons 6266.4 Unimolecular photochemical reactions of carbonyl compounds 6376.5 Unimolecular photoreactions of benzene and heteroaromatic analogs 6446.6 Photocleavage of carbon–heteroatom bonds 6496.7 Photocleavage of nitrogen—nitrogen bonds 6616.8 Photochemical cycloadditions of unsaturated compounds 6676.9 Photo-oxygenation 6886.10 Photoinduced electron transfers 7106.11 Chemiluminescence and bioluminescence 7277 Catalytic reactions 7957.1 Introduction 7957.2 Acyl group transfers 7987.3 Catalysis of nucleophilic additions 8107.4 Anionic nucleophilic displacement reactions 8157.5 Catalytical Umpolung C—C bond forming reactions 8187.6 Brønsted and Lewis acids as catalysts in C—C bond forming reactions 8367.7 Bonding in transition metal complexes and their reactions 8587.8 Catalytic hydrogenation 8917.9 Catalytic reactions of silanes 9067.10 Hydrogenolysis of C—C single bonds 9107.11 Catalytic oxidations with molecular oxygen 9117.12 Catalyzed nucleophilic aromatic substitutions 9228 Transition-metal-catalyzed C—C bond forming reactions 10298.1 Introduction 10298.2 Organic compounds from carbon monoxide 10308.3 Direct hydrocarbation of unsaturated compounds 10538.4 Carbacarbation of unsaturated compounds and cycloadditions 10708.5 Didehydrogenative C—C-coupling reactions 11168.6 Alkane, alkene, and alkyne metathesis 11248.7 Additions of organometallic reagents 11348.8 Displacement reactions 1148References 1191Index 1317Organic Chemistry Workbook: Theory, Reactivity and Mechanisms in Modern Synthesis1 Equilibria and Thermochemistry 1Answers to Problems 1References 252 Additivity Rules for Thermodynamical Parameters and Deviations 27Answers to Problems 27References 603 The Rates of Chemical Reactions 61Answers to Problems 613.1 Additional Material 793.1.1 The Bell–Evans–Polanyi Theory for Radical Exchanges 793.1.2 The Effect of Reactant Polarizability 803.1.3 The Effect of Exothermicity 823.1.4 The Hammond–Leffler Postulate is a Theorem Demonstrated by the Bell–Evans–Polanyi Theory 833.1.5 The Selectivity/Reactivity Relationship 84References 854 Molecular Orbital Theories 89Answers to Problems 89References 975 Pericyclic Reactions 99Answers to Problems 99Additional Material 148References 1496 Organic Photochemistry 153Answers to Problems 153Additional Material 191References 1927 Catalytic Reactions 197Answers to Problems 197References 2208 Transition-Metal-Catalyzed C—C Bond Forming Reactions 223Answers to Problems 223References 278

Pierre Vogel is Professor of organic chemistry at the EPFL in Lausanne, Switzerland. He has published three books and has co-authored more than 490 publications in the fields of physical organic chemistry, organic and organometallic synthesis, total asymmetric synthesis of natural products of biological interest, catalysis, glycochemistry and bio-organic chemistry.Kendall N. Houk is Saul Winstein Professor at the UCLA. He is an authority on theoretical and computational organic chemistry. His group develops rules to understand reactivity, computationally models complex organic reactions, and experimentally tests the predictions of theory. He collaborates prodigiously with chemists all over the world. He has published nearly 1100 articles in refereed journals and is among the 100 most-cited chemists.

• Organic Chemistry: Theory, Reactivity and Mechanisms in Modern SynthesisPreface xvForeword xxix1 Equilibria and thermochemistry 11.1 Introduction 11.2 Equilibrium-free enthalpy: reaction-free energy or Gibbs energy 11.3 Heat of reaction and variation of the entropy of reaction (reaction entropy) 21.4 Statistical thermodynamics 41.5 Standard heats of formation 81.6 What do standard heats of formation tell us about chemical bonding and ground-state properties of organic compounds? 91.7 Standard heats of typical organic reactions 141.8 Ionization energies and electron affinities 201.9 Homolytic bond dissociations; heats of formation of radicals 221.10 Heterolytic bond dissociation enthalpies 281.11 Electron transfer equilibria 321.12 Heats of formation of neutral, transient compounds 321.13 Electronegativity and absolute hardness 371.14 Chemical conversion and selectivity controlled by thermodynamics 401.15 Thermodynamic (equilibrium) isotopic effects 492 Additivity rules for thermodynamic parameters and deviations 1092.1 Introduction 1092.2 Molecular groups 1102.3 Determination of the standard group equivalents (group equivalents) 1112.4 Determination of standard entropy increments 1132.5 Steric effects 1142.6 Ring strain and conformational flexibility of cyclic compounds 1172.7 ;;/π-, n/π-, σ/π-, and n/σ-interactions 1272.8 Other deviations to additivity rules 1442.9 Major role of translational entropy on equilibria 1462.10 Entropy of cyclization: loss of degrees of free rotation 1512.11 Entropy as a synthetic tool 1513 Rates of chemical reactions 1773.1 Introduction 1773.2 Differential and integrated rate laws 1773.3 Activation parameters 1883.4 Relationship between activation entropy and the reaction mechanism 1923.5 Competition between cyclization and intermolecular condensation 1973.6 Effect of pressure: activation volume 2013.7 Asymmetric organic synthesis 2063.8 Chemo- and site-selective reactions 2293.9 Kinetic isotope effects and reaction mechanisms 2314 Molecular orbital theories 271.1 Introduction 2714.2 Background of quantum chemistry 2714.3 Schrödinger equation 2724.4 Coulson and Longuet-Higgins approach 2744.5 Hückel method 2774.6 Aromatic stabilization energy of heterocyclic compounds 3054.7 Homoconjugation 3084.8 Hyperconjugation 3144.9 Heilbronner Möbius aromatic [N]annulenes 3244.10 Conclusion 3265 Pericyclic reactions 3395.1 Introduction 3395.2 Electrocyclic reactions 3405.3 Cycloadditions and cycloreversions 3615.4 Cheletropic reactions 4375.5 Thermal sigmatropic rearrangements 4515.6 Dyotropic rearrangements and transfers 4955.7 Ene-reactions and related reactions 5006 Organic photochemistry 6156.1 Introduction 6156.2 Photophysical processes of organic compounds 6156.3 Unimolecular photochemical reactions of unsaturated hydrocarbons 6266.4 Unimolecular photochemical reactions of carbonyl compounds 6376.5 Unimolecular photoreactions of benzene and heteroaromatic analogs 6446.6 Photocleavage of carbon–heteroatom bonds 6496.7 Photocleavage of nitrogen—nitrogen bonds 6616.8 Photochemical cycloadditions of unsaturated compounds 6676.9 Photo-oxygenation 6886.10 Photoinduced electron transfers 7106.11 Chemiluminescence and bioluminescence 7277 Catalytic reactions 7957.1 Introduction 7957.2 Acyl group transfers 7987.3 Catalysis of nucleophilic additions 8107.4 Anionic nucleophilic displacement reactions 8157.5 Catalytical Umpolung C—C bond forming reactions 8187.6 Brønsted and Lewis acids as catalysts in C—C bond forming reactions 8367.7 Bonding in transition metal complexes and their reactions 8587.8 Catalytic hydrogenation 8917.9 Catalytic reactions of silanes 9067.10 Hydrogenolysis of C—C single bonds 9107.11 Catalytic oxidations with molecular oxygen 9117.12 Catalyzed nucleophilic aromatic substitutions 9228 Transition-metal-catalyzed C—C bond forming reactions 10298.1 Introduction 10298.2 Organic compounds from carbon monoxide 10308.3 Direct hydrocarbation of unsaturated compounds 10538.4 Carbacarbation of unsaturated compounds and cycloadditions 10708.5 Didehydrogenative C—C-coupling reactions 11168.6 Alkane, alkene, and alkyne metathesis 11248.7 Additions of organometallic reagents 11348.8 Displacement reactions 1148References 1191Index 1317Organic Chemistry Workbook: Theory, Reactivity and Mechanisms in Modern Synthesis1 Equilibria and Thermochemistry 1Answers to Problems 1References 252 Additivity Rules for Thermodynamical Parameters and Deviations 27Answers to Problems 27References 603 The Rates of Chemical Reactions 61Answers to Problems 613.1 Additional Material 793.1.1 The Bell–Evans–Polanyi Theory for Radical Exchanges 793.1.2 The Effect of Reactant Polarizability 803.1.3 The Effect of Exothermicity 823.1.4 The Hammond–Leffler Postulate is a Theorem Demonstrated by the Bell–Evans–Polanyi Theory 833.1.5 The Selectivity/Reactivity Relationship 84References 854 Molecular Orbital Theories 89Answers to Problems 89References 975 Pericyclic Reactions 99Answers to Problems 99Additional Material 148References 1496 Organic Photochemistry 153Answers to Problems 153Additional Material 191References 1927 Catalytic Reactions 197Answers to Problems 197References 2208 Transition-Metal-Catalyzed C—C Bond Forming Reactions 223Answers to Problems 223References 278