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Organic Chemistry: Theory, Reactivity and Mechanisms in Modern Synthesis, Deluxe Edition
The know-how about reactivity, reaction mechanisms, thermodynamics and other basics in physical organic chemistry is the key for successful organic reactions. This textbook with its workbook presents comprehensively this knowledge to the student and to the researcher, too.
Contents
Organic Chemistry: Theory, Reactivity and Mechanisms in Modern Synthesis
Preface xv
Foreword xxix
1 Equilibria and thermochemistry 1
1.1 Introduction 1
1.2 Equilibrium-free enthalpy: reaction-free energy or Gibbs energy 1
1.3 Heat of reaction and variation of the entropy of reaction (reaction entropy) 2
1.4 Statistical thermodynamics 4
1.5 Standard heats of formation 8
1.6 What do standard heats of formation tell us about chemical bonding and ground-state properties of organic compounds? 9
1.7 Standard heats of typical organic reactions 14
1.8 Ionization energies and electron affinities 20
1.9 Homolytic bond dissociations; heats of formation of radicals 22
1.10 Heterolytic bond dissociation enthalpies 28
1.11 Electron transfer equilibria 32
1.12 Heats of formation of neutral, transient compounds 32
1.13 Electronegativity and absolute hardness 37
1.14 Chemical conversion and selectivity controlled by thermodynamics 40
1.15 Thermodynamic (equilibrium) isotopic effects 49
2 Additivity rules for thermodynamic parameters and deviations 109
2.1 Introduction 109
2.2 Molecular groups 110
2.3 Determination of the standard group equivalents (group equivalents) 111
2.4 Determination of standard entropy increments 113
2.5 Steric effects 114
2.6 Ring strain and conformational flexibility of cyclic compounds 117
2.7 ;;/π-, n/π-, σ/π-, and n/σ-interactions 127
2.8 Other deviations to additivity rules 144
2.9 Major role of translational entropy on equilibria 146
2.10 Entropy of cyclization: loss of degrees of free rotation 151
2.11 Entropy as a synthetic tool 151
3 Rates of chemical reactions 177
3.1 Introduction 177
3.2 Differential and integrated rate laws 177
3.3 Activation parameters 188
3.4 Relationship between activation entropy and the reaction mechanism 192
3.5 Competition between cyclization and intermolecular condensation 197
3.6 Effect of pressure: activation volume 201
3.7 Asymmetric organic synthesis 206
3.8 Chemo- and site-selective reactions 229
3.9 Kinetic isotope effects and reaction mechanisms 231
4 Molecular orbital theories 271
.1 Introduction 271
4.2 Background of quantum chemistry 271
4.3 Schrödinger equation 272
4.4 Coulson and Longuet-Higgins approach 274
4.5 Hückel method 277
4.6 Aromatic stabilization energy of heterocyclic compounds 305
4.7 Homoconjugation 308
4.8 Hyperconjugation 314
4.9 Heilbronner Möbius aromatic [N]annulenes 324
4.10 Conclusion 326
5 Pericyclic reactions 339
5.1 Introduction 339
5.2 Electrocyclic reactions 340
5.3 Cycloadditions and cycloreversions 361
5.4 Cheletropic reactions 437
5.5 Thermal sigmatropic rearrangements 451
5.6 Dyotropic rearrangements and transfers 495
5.7 Ene-reactions and related reactions 500
6 Organic photochemistry 615
6.1 Introduction 615
6.2 Photophysical processes of organic compounds 615
6.3 Unimolecular photochemical reactions of unsaturated hydrocarbons 626
6.4 Unimolecular photochemical reactions of carbonyl compounds 637
6.5 Unimolecular photoreactions of benzene and heteroaromatic analogs 644
6.6 Photocleavage of carbon-heteroatom bonds 649
6.7 Photocleavage of nitrogen—nitrogen bonds 661
6.8 Photochemical cycloadditions of unsaturated compounds 667
6.9 Photo-oxygenation 688
6.10 Photoinduced electron transfers 710
6.11 Chemiluminescence and bioluminescence 727
7 Catalytic reactions 795
7.1 Introduction 795
7.2 Acyl group transfers 798
7.3 Catalysis of nucleophilic additions 810
7.4 Anionic nucleophilic displacement reactions 815
7.5 Catalytical Umpolung C—C bond forming reactions 818
7.6 Brønsted and Lewis acids as catalysts in C—C bond forming reactions 836
7.7 Bonding in transition metal complexes and their reactions 858
7.8 Catalytic hydrogenation 891
7.9 Catalytic reactions of silanes 906
7.10 Hydrogenolysis of C—C single bonds 910
7.11 Catalytic oxidations with molecular oxygen 911
7.12 Catalyzed nucleophilic aromatic substitutions 922
8 Transition-metal-catalyzed C—C bond forming reactions 1029
8.1 Introduction 1029
8.2 Organic compounds from carbon monoxide 1030
8.3 Direct hydrocarbation of unsaturated compounds 1053
8.4 Carbacarbation of unsaturated compounds and cycloadditions 1070
8.5 Didehydrogenative C—C-coupling reactions 1116
8.6 Alkane, alkene, and alkyne metathesis 1124
8.7 Additions of organometallic reagents 1134
8.8 Displacement reactions 1148
References 1191
Index 1317
Organic Chemistry Workbook: Theory, Reactivity and Mechanisms in Modern Synthesis
1 Equilibria and Thermochemistry 1
Answers to Problems 1
References 25
2 Additivity Rules for Thermodynamical Parameters and Deviations 27
Answers to Problems 27
References 60
3 The Rates of Chemical Reactions 61
Answers to Problems 61
3.1 Additional Material 79
3.1.1 The Bell-Evans-Polanyi Theory for Radical Exchanges 79
3.1.2 The Effect of Reactant Polarizability 80
3.1.3 The Effect of Exothermicity 82
3.1.4 The Hammond-Leffler Postulate is a Theorem Demonstrated by the Bell-Evans-Polanyi Theory 83
3.1.5 The Selectivity/Reactivity Relationship 84
References 85
4 Molecular Orbital Theories 89
Answers to Problems 89
References 97
5 Pericyclic Reactions 99
Answers to Problems 99
Additional Material 148
References 149
6 Organic Photochemistry 153
Answers to Problems 153
Additional Material 191
References 192
7 Catalytic Reactions 197
Answers to Problems 197
References 220
8 Transition-Metal-Catalyzed C—C Bond Forming Reactions 223
Answers to Problems 223
References 278
