Description
JOHN WILEY Organic Chemistry Theory Reactivity And Mechanisms In Modern Synthesis 2019 Edition by Pierre Vogel, Kendall N. Houk
Provides the background, tools, and models required to understand organic synthesis and plan chemical reactions more efficientlyKnowledge of physical chemistry is essential for achieving successful chemical reactions in organic chemistry. Chemists must be competent in a range of areas to understand organic synthesis. Organic Chemistry provides the methods, models, and tools necessary to fully comprehend organic reactions. Written by two internationally recognized experts in the field, this much-needed textbook fills a gap in current literature on physical organic chemistry. Rigorous yet straightforward chapters first examine chemical equilibria, thermodynamics, reaction rates and mechanisms, and molecular orbital theory, providing readers with a strong foundation in physical organic chemistry. Subsequent chapters demonstrate various reactions involving organic, organometallic, and biochemical reactants and catalysts. Throughout the text, numerous questions and exercises, over 800 in total, help readers strengthen their comprehension of the subject and highlight key points of learning. The companion Organic Chemistry Workbook contains complete references and answers to every question in this text. A much-needed resource for students and working chemists alike, this text:-Presents models that establish if a reaction is possible, estimate how long it will take, and determine its properties -Describes reactions with broad practical value in synthesis and biology, such as C-C-coupling reactions, pericyclic reactions, and catalytic reactions-Enables readers to plan chemical reactions more efficiently-Features clear illustrations, figures, and tables-With a Foreword by Nobel Prize Laureate Robert H. GrubbsOrganic Chemistry: Theory, Reactivity, and Mechanisms in Modern Synthesis is an ideal textbook for students and instructors of chemistry, and a valuable work of reference for organic chemists, physical chemists, and chemical engineers. Preface 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 41.4.1 Contributions from translation energy levels 51.4.2 Contributions from rotational energy levels 51.4.3 Contributions from vibrational energy levels 61.4.4 Entropy of reaction depends above all on the change of the number of molecules between products and reactants 71.4.5 Additions are favored thermodynamically on cooling, fragmentations on heating 71.5 Standard heats of formation 81.6 What do standard heats of formation tell us about chemical bonding and ground-state properties of organic compounds? 91.6.1 Effect of electronegativity on bond strength 101.6.2 Effects of electronegativity and of hyperconjugation 111.6.3 -Conjugation and hyperconjugation in carboxylic functions 121.6.4 Degree of chain branching and Markovnikov's rule 131.7 Standard heats of typical organic reactions 141.7.1 Standard heats of hydrogenation and hydrocarbation 141.7.2 Standard heats of C-H oxidations 151.7.3 Relative stabilities of alkyl-substituted ethylenes 171.7.4 Effect of fluoro substituents on hydrocarbon stabilities 171.7.5 Storage of hydrogen in the form of formic acid 181.8 Ionization energies and electron affinities 201.9 Homolytic bond dissociations; heats of formation of radicals 221.9.1 Measurement of bond dissociation energies 221.9.2 Substituent effects on the relative stabilities of radicals 251.9.3 -Conjugation in benzyl, allyl, and propargyl radicals 251.10 Heterolytic bond dissociation enthalpies 281.10.1 Measurement of gas-phase heterolytic bond dissociation enthalpies 281.10.2 Thermochemistry of ions in the gas phase 291.10.3 Gas-phase acidities 301.11 Electron transfer equilibria 321.12 Heats of formation of neutral, transient compounds 321.12.1 Measurements of the heats of formation of carbenes 321.12.2 Measurements of the heats of formation of diradicals 331.12.3 Keto/enol tautomerism 331.12.4 Heat of formation of highly reactive cyclobutadiene 361.12.5 Estimate of heats of formation of diradicals 361.13 Electronegativity and absolute hardness 371.14 Chemical conversion and selectivity controlled by thermodynamics 401.14.1 Equilibrium shifts (Le Chatelier's principle in action) 401.14.2 Importance of chirality in biology and medicine 411.14.3 Resolution of racemates into enantiomers 431.14.4 Thermodynamically controlled deracemization 461.14.5 Self-disproportionation of enantiomers 481.15 Thermodynamic (equilibrium) isotopic effects 491.A Appendix, Table 1.A.1 to Table 1.A.24 53References 922 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 1142.5.1 Gauche interactions: the preferred conformations of alkyl chains 1142.5.2 (E)- vs. (Z)-alkenes and ortho-substitution in benzene derivatives 1172.6 Ring strain and conformational flexibility of cyclic compounds 1172.6.1 Cyclopropane and cyclobutane have nearly the same strain energy 1182.6.2 Cyclopentane is a flexible cycloalkane 1192.6.3 Conformational analysis of cyclohexane 1192.6.4 Conformational analysis of cyclohexanones 1212.6.5 Conformational analysis of cyclohexene 1222.6.6 Medium-sized cycloalkanes 1222.6.7 Conformations and ring strain in polycycloalkanes 1242.6.8 Ring strain in cycloalkenes 1252.6.9 Bredt's rule and "anti-Bredt" alkenes 1252.6.10 Allylic 1,3- and 1,2-strain: the model of banana bonds 1262.7 ?/ -, n/ -, / -, and n/ -interactions 1272.7.1 Conjugated dienes and diynes 1272.7.2 Atropisomerism in 1,3-dienes and diaryl compounds 1292.7.3 ?, -Unsaturated carbonyl compounds 1302.7.4 Stabilization by aromaticity 1302.7.5 Stabilization by n(Z:)/? conjugation 1322.7.6 ?/ -Conjugation and ?/ -hyperconjugation in esters, thioesters, and amides 1332.7.7 Oximes are more stable than imines toward hydrolysis 1362.7.8 Aromatic stabilization energies of heterocyclic compounds 1362.7.9 Geminal disubstitution: enthalpic anomeric effects 1392.7.10 Conformational anomeric effect 1412.8 Other deviations to additivity rules 1442.9 Major role of translational entropy on equilibria 1462.9.1 Aldol and crotonalization reactions 1462.9.2 Aging of wines 1482.10 Entropy of cyclization: loss of degrees of free rotation 1512.11 Entropy as a synthetic tool 1512.11.1 Pyrolysis of esters 1512.11.2 Method of Chugaev 1522.11.3 Eschenmoser-Tanabe fragmentation 1522.11.4 Eschenmoser fragmentation 1532.11.5 Thermal 1,4-eliminations 1532.11.6 Retro-Diels-Alder reactions 1562.A Appendix, Table 2.A.1 to Table 2.A.2 157References 1613 Rates of chemical reactions 1773.1 Introduction 1773.2 Differential and integrated rate laws 1773.2.1 Order of reactions 1783.2.2 Molecularity and reaction mechanisms 1793.2.3 Examples of zero order reactions 1813.2.4 Reversible reactions 1823.2.5 Parallel reactions 1833.2.6 Consecutive reactions and steady-state approximation 1833.2.7 Consecutive reactions: maximum yield of the intermediate product 1843.2.8 Homogeneous catalysis: Michaelis-Menten kinetics 1853.2.9 Competitive vs. noncompetitive inhibition 1863.2.10 Heterogeneous catalysis: reactions at surfaces 1873.3 Activation parameters 1883.3.1 Temperature effect on the selectivity of two parallel reactions 1903.3.2 The Curtin-Hammett principle 1903.4 Relationship between activation entropy and the reaction mechanism 1923.4.1 Homolysis and radical combination in the gas phase 1923.4.2 Isomerizations in the gas phase 1933.4.3 Example of homolysis assisted by bond formation: the Cope rearrangement 1953.4.4 Example of homolysis assisted by bond-breaking and bond-forming processes: retro-carbonyl-ene reaction 1953.4.5 Can a reaction be assisted by neighboring groups? 1973.5 Competition between cyclization and intermolecular condensation 1973.5.1 Thorpe-Ingold effect 1983.6 Effect of pressure: activation volume 2013.6.1 Relationship between activation volume and the mechanism of reaction 2013.6.2 Detection of change of mechanism 2023.6.3 Synthetic applications of high pressure 2033.6.4 Rate enhancement by compression of reactants along the reaction coordinates 2043.6.5 Structural effects on the rate of the Bergman rearrangement 2053.7 Asymmetric organic synthesis 2063.7.1 Kinetic resolution 2063.7.2 Parallel kinetic resolution 2113.7.3 Dynamic kinetic resolution: kinetic deracemization 2123.7.4 Synthesis starting from enantiomerically pure natural compounds 2153.7.5 Use of recoverable chiral auxiliaries 2173.7.6 Catalytic desymmetrization of achiral compounds 2203.7.7 Nonlinear effects in asymmetric synthesis 2263.7.8 Asymmetric autocatalysis 2283.8 Chemo- and site-selective reactions 2293.9 Kinetic isotope effects and reaction mechanisms 2313.9.1 Primary kinetic isotope effects: the case of hydrogen transfers 2313.9.2 Tunneling effects 2323.9.3 Nucleophilic substitution and elimination reactions 2343.9.4 Steric effect on kinetic isotope effects 2393.9.5 Simultaneous determination of multiple small kinetic isotope effects at natural abundance 239References 2404 Molecular orbital theories 2714.1 Introduction 2714.2 Background of quantum chemistry 2714.3 Schroedinger equation 2724.4 Coulson and Longuet-Higgins approach 2744.4.1 Hydrogen molecule 2754.4.2 Hydrogenoid molecules: The PMO theory 2764.5 Huckel method 2774.5.1 -Molecular orbitals of ethylene 2784.5.2 Allyl cation, radical, and anion 2794.5.3 Shape of allyl -molecular orbitals 2824.5.4 Cyclopropenyl systems 2824.5.5 Butadiene 2854.5.6 Cyclobutadiene and its electronic destabilization (antiaromaticity) 2864.5.7 Geometries of cyclobutadienes, singlet and triplet states 2884.5.8 Pentadienyl and cyclopentadienyl systems 2914.5.9 Cyclopentadienyl anion and bishomocyclopentadienyl anions 2924.5.10 Benzene and its aromatic stabilization energy 2944.5.11 3,4-Dimethylidenecyclobutene is not stabilized by -conjugation 2954.5.12 Fulvene 2974.5.13 [N]Annulenes 2984.5.14 Cyclooctatetraene 3014.5.15 -systems with heteroatoms 3024.6 Aromatic stabilization energy of heterocyclic compounds 3054.7 Homoconjugation 3084.7.1 Homoaromaticity in cyclobutenyl cation 3084.7.2 Homoaromaticity in homotropylium cation 3084.7.3 Homoaromaticity in cycloheptatriene 3104.7.4 Bishomoaromaticity in bishomotropylium ions 3114.7.5 Bishomoaromaticity in neutral semibullvalene derivatives 3124.7.6 Barrelene effect 3134.8 Hyperconjugation 3144.8.1 Neutral, positive, and negative hyperconjugation 3144.8.2 Hyperconjugation in cyclopentadienes 3154.8.3 Nonplanarity of bicyclo[2.2.1]hept-2-ene double bond 3154.8.4 Conformation of unsaturated and saturated systems 3174.8.5 Hyperconjugation in radicals 3194.8.6 Hyperconjugation in carbenium ions 3204.8.7 Hyperconjugation in carbanions 3204.8.8 Cyclopropyl vs. cyclobutyl substituent effect 3224.9 Heilbronner Moebius aromatic [N]annulenes 3244.10 Conclusion 326References 3265 Pericyclic reactions 3395.1 Introduction 3395.2 Electrocyclic reactions 3405.2.1 Stereochemistry of thermal cyclobutene-butadiene isomerization: four-electron electrocyclic reactions 3405.2.2 Longuet-Higgins correlation of electronic configurations 3425.2.3 Woodward-Hoffmann simplification 3455.2.4 Aromaticity of transition states in cyclobutene/butadiene electrocyclizations 3465.2.5 Torquoselectivity of cyclobutene electrocyclic reactions 3475.2.6 Nazarov cyclizations 3505.2.7 Thermal openings of three-membered ring systems 3545.2.8 Six-electron electrocyclic reactions 3575.2.9 Eight-electron electrocyclic reactions 3605.3 Cycloadditions and cycloreversions 3615.3.1 Stereoselectivity of thermal [?2+?2]-cycloadditions: Longuet-Higgins model 3625.3.2 Woodward-Hoffmann rules for cycloadditions 3645.3.3 Aromaticity of cycloaddition transition structures 3665.3.4 Mechanism of thermal [?2+?2]-cycloadditions and [?2+?2]-cycloreversions: 1,4- diradical/zwitterion intermediates or diradicaloid transition structures 3685.3.5 Cycloadditions of allenes 3725.3.6 Cycloadditions of ketenes and keteniminium salts 3735.3.7 Wittig olefination 3805.3.8 Olefinations analogous to the Wittig reaction 3845.3.9 Diels-Alder reaction: concerted and non-concerted mechanisms compete 3875.3.10 Concerted Diels-Alder reactions with synchronous or asynchronous transition states 3915.3.11 Diradicaloid model for transition states of concerted Diels-Alder reactions 3925.3.12 Structural effects on the Diels-Alder reactivity 3975.3.13 Regioselectivity of Diels-Alder reactions 3995.3.14 Stereoselectivity of Diels-Alder reactions: the Alder "endo rule" 4065.3.15 -Facial selectivity of Diels-Alder reactions 4085.3.16 Examples of hetero-Diels-Alder reactions 4115.3.17 1,3-Dipolar cycloadditions 4205.3.18 Sharpless asymmetric dihydroxylation of alkenes 4285.3.19 Thermal (2+2+2)-cycloadditions 4285.3.20 Noncatalyzed (4+3)- and (5+2)-cycloadditions 4315.3.21 Thermal higher order (m+n)-cycloadditions 4345.4 Cheletropic reactions 4375.4.1 Cyclopropanation by (2+1)-cheletropic reaction of carbenes 4375.4.2 Aziridination by (2+1)-cheletropic addition of nitrenes 4405.4.3 Decarbonylation of cyclic ketones by cheletropic elimination 4425.4.4 Cheletropic reactions of sulfur dioxide 4445.4.5 Cheletropic reactions of heavier congeners of carbenes and nitrenes 4475.5 Thermal sigmatropic rearrangements 4515.5.1 (1,2)-Sigmatropic rearrangement of carbenium ions 4515.5.2 (1,2)-Sigmatropic rearrangements of radicals 4565.5.3 (1,2)-Sigmatropic rearrangements of organoalkali compounds 4595.5.4 (1,3)-Sigmatropic rearrangements 4625.5.5 (1,4)-Sigmatropic rearrangements 4655.5.6 (1,5)-Sigmatropic rearrangements 4675.5.7 (1,7)-Sigmatropic rearrangements 4695.5.8 (2,3)-Sigmatropic rearrangements 4705.5.9 (3,3)-Sigmatropic rearrangements 4765.5.9.1 Fischer indole synthesis (3,4-diaza-Cope rearrangement) 4765.5.9.2 Claisen rearrangement and its variants (3-oxa-Cope rearrangements) 4765.5.9.3 Aza-Claisen rearrangements (3-aza-Cope rearrangements) 4815.5.9.4 Overman rearrangement (1-oxa-3-aza-Cope rearrangement) 4835.5.9.5 Thia-Claisen rearrangement (3-thia-Cope rearrangement) 4845.5.9.6 Cope rearrangements 4845.5.9.7 Facile anionic oxy-Cope rearrangements 4895.5.9.8 Acetylenic Cope rearrangements 4915.5.9.9 Other hetero-Cope rearrangements 4925.6 Dyotropic rearrangements and transfers 4955.6.1 Type I dyotropic rearrangements 4965.6.2 Alkene and alkyne reductions with diimide 4985.6.3 Type II dyotropic rearrangements 4995.7 Ene-reactions and related reactions 5005.7.1 Thermal Alder ene-reactions 5015.7.2 Carbonyl ene-reactions 5045.7.3 Other hetero-ene reactions involving hydrogen transfers 5045.7.4 Metallo-ene-reactions 5085.7.5 Carbonyl allylation with allylmetals: carbonyl metallo-ene-reactions 5095.7.6 Aldol reaction 5145.7.7 Reactions of metal enolates with carbonyl compounds 518References 5266 Organic photochemistry 6156.1 Introduction 6156.2 Photophysical processes of organic compounds 6156.2.1 UV-visible spectroscopy: electronic transitions 6166.2.2 Fluorescence and phosphorescence: singlet and triplet excited states 6206.2.3 Bimolecular photophysical processes 6236.3 Unimolecular photochemical reactions of unsaturated hydrocarbons 6266.3.1 Photoinduced (E)/(Z)-isomerization of alkenes 6266.3.2 Photochemistry of cyclopropenes, allenes, and alkynes 6306.3.3 Electrocyclic ring closures of conjugated dienes and ring opening of cyclobutenes 6316.3.4 The di- -methane (Zimmerman) rearrangement of 1,4-dienes 6336.3.5 Electrocyclic interconversions of cyclohexa-1,3-dienes and hexa-1,3,5-trienes 6356.4 Unimolecular photochemical reactions of carbonyl compounds 6376.4.1 Norrish type I reaction ( -cleavage) 6376.4.2 Norrish type II reaction and other intramolecular hydrogen transfers 6396.4.3 Unimolecular photochemistry of enones and dienones 6426.5 Unimolecular photoreactions of benzene and heteroaromatic analogs 6446.5.1 Photoisomerization of benzene 6446.5.2 Photoisomerizations of pyridines, pyridinium salts, and diazines 6466.5.3 Photolysis of five-membered ring heteroaromatic compounds 6476.6 Photocleavage of carbon-heteroatom bonds 6496.6.1 Photo-Fries, photo-Claisen, and related rearrangements 6496.6.2 Photolysis of 1,2-diazenes, 3H-diazirines, and diazo compounds 6516.6.3 Photolysis of alkyl halides 6546.6.4 Solution photochemistry of aryl and alkenyl halides 6576.6.5 Photolysis of phenyliodonium salts: formation of aryl and alkenyl cation intermediates 6596.6.6 Photolytic decomposition of arenediazonium salts in solution 6606.7 Photocleavage of nitrogen-nitrogen bonds 6616.7.1 Photolysis of azides 6626.7.2 Photo-Curtius rearrangement 6646.7.3 Photolysis of geminal diazides 6656.7.4 Photolysis of 1,2,3-triazoles and of tetrazoles 6666.8 Photochemical cycloadditions of unsaturated compounds 6676.8.1 Photochemical intramolecular (2+2)-cycloadditions of alkenes 6686.8.2 Photochemical intermolecular (2+2)-cycloadditions of alkenes 6726.8.3 Photochemical intermolecular (4+2)-cycloadditions of dienes and alkenes 6766.8.4 Photochemical cycloadditions of benzene and derivatives to alkenes 6776.8.5 Photochemical cycloadditions of carbonyl compounds 6816.8.6 Photochemical cycloadditions of imines and related C=N double-bonded compounds 6866.9 Photo-oxygenation 6886.9.1 Reactions of ground-state molecular oxygen with hydrocarbons 6886.9.2 Singlet molecular oxygen 6916.9.3 Diels-Alder reactions of singlet oxygen 6956.9.4 Dioxa-ene reactions of singlet oxygen 7006.9.5 (2+2)-Cycloadditions of singlet oxygen 7046.9.6 1,3-Dipolar cycloadditions of singlet oxygen 7056.9.7 Nonpericyclic reactions of singlet oxygen 7076.10 Photoinduced electron transfers 7106.10.1 Marcus model 7116.10.2 Catalysis through photoreduction 7116.10.3 Photoinduced net reductions 7156.10.4 Catalysis through photo-oxidation 7176.10.5 Photoinduced net oxidations 7216.10.6 Generation of radical intermediates by PET 7246.10.7 Dye-sensitized solar cells 7266.11 Chemiluminescence and bioluminescence 7276.11.1 Thermal isomerization of Dewar benzene into benzene 7286.11.2 Oxygenation of electron-rich organic compounds 7296.11.3 Thermal fragmentation of 1,2-dioxetanes 7326.11.4 Peroxylate chemiluminescence 7346.11.5 Firefly bioluminescence 734References 7357 Catalytic reactions 7957.1 Introduction 7957.2 Acyl group transfers 7987.2.1 Esterification and ester hydrolysis 7987.2.2 Acid or base-catalyzed acyl transfers 7997.2.3 Amphoteric compounds are good catalysts for acyl transfers 8027.2.4 Catalysis by nucleofugal group substitution 8027.2.5 N-heterocyclic carbene-catalyzed transesterifications 8047.2.6 Enzyme-catalyzed acyl transfers 8067.2.7 Mimics of carboxypeptidase A 8077.2.8 Direct amide bond formation from amines and carboxylic acids 8077.3 Catalysis of nucleophilic additions 8107.3.1 Catalysis of nucleophilic additions to aldehydes, ketones and imines 8107.3.2 Bifunctional catalysts for nucleophilic addition/elimination 8117.3.3 - and -Nucleophiles as catalysts for nucleophilic additions to aldehydes and ketones 8127.3.4 Catalysis by self-assembled encapsulation 8137.3.5 Catalysis of 1,4-additions (conjugate additions) 8147.4 Anionic nucleophilic displacement reactions 8157.4.1 Pulling on the leaving group 8157.4.2 Phase transfer catalysis 8167.5 Catalytical Umpolung C-C bond forming reactions 8187.5.1 Benzoin condensation: Umpolung of aldehydes 8197.5.2 Stetter reaction: Umpolung of aldehydes 8217.5.3 Umpolung of enals 8227.5.4 Umpolung of Michael acceptors 8237.5.5 Rauhut-Currier reaction 8267.5.6 Morita-Baylis-Hillman reaction 8267.5.7 Nucleophilic catalysis of cycloadditions 8287.5.8 Catalysis through electron-transfer: hole-catalyzed reactions 8317.5.9 Umpolung of enamines 8347.5.10 Catalysis through electron-transfer: Umpolung through electron capture 8367.6 Bronsted and Lewis acids as catalysts in C-C bond forming reactions 8367.6.1 Mukaiyama aldol reactions 8397.6.2 Metallo-carbonyl-ene reactions 8437.6.3 Carbonyl-ene reactions 8467.6.4 Imine-ene reactions 8477.6.5 Alder-ene reaction 8487.6.6 Diels-Alder reaction 8497.6.7 Bronsted and Lewis acid-catalyzed hetero-Diels-Alder reactions 8517.6.8 Acid-catalyzed (2+2)-cycloadditions 8537.6.9 Lewis acid catalyzed (3+2)- and (3+3)-cycloadditions 8557.6.10 Lewis acid promoted (5+2)-cycloadditions 8577.7 Bonding in transition metal complexes and their reactions 8587.7.1 The -complex theory 8587.7.2 The isolobal formalism 8607.7.3 -Complexes of dihydrogen 8637.7.4 -Complexes of C-H bonds and agostic bonding 8667.7.5 -Complexes of C-C bonds and C-C bond activation 8677.7.6 Reactions of transition metal complexes are modeled by reactions of organic chemistry 8697.7.7 Ligand exchange reactions 8697.7.8 Oxidative additions and reductive eliminations 8737.7.9 -Insertions/ -eliminations 8807.7.10 -Insertions/ -eliminations 8837.7.11 -Cycloinsertions/ -cycloeliminations: metallacyclobutanes, metallacyclobutenes 8867.7.12 Metallacyclobutenes: alkyne polymerization, enyne metathesis, cyclopentadiene synthesis 8877.7.13 Metallacyclobutadiene: alkyne metathesis 8897.7.14 Matallacyclopentanes, metallacyclopentenes, metallacyclopentadienes: oxidative cyclizations( -cycloinsertions) and reductive fragmentations ( -cycloeliminations) 8907.8 Catalytic hydrogenation 8917.8.1 Heterogeneous catalysts for alkene, alkyne, and arene hydrogenation 8927.8.2 Homogeneous catalysts for alkene and alkyne hydrogenation 8947.8.3 Dehydrogenation of alkanes 8977.8.4 Hydrogenation of alkynes into alkenes 8977.8.5 Catalytic hydrogenation of arenes and heteroarenes 8997.8.6 Catalytic hydrogenation of ketones and aldehydes 8997.8.7 Catalytic hydrogenation of carboxylic acids, their esters and amides 9027.8.8 Hydrogenation of carbon dioxide 9037.8.9 Catalytic hydrogenation of nitriles and imines 9047.8.10 Catalytic hydrogenolysis of C-halogen and C-chalcogen bonds 9067.9 Catalytic reactions of silanes 9067.9.1 Reduction of alkyl halides 9067.9.2 Reduction of carbonyl compounds 9077.9.3 Alkene hydrosilylation 9097.10 Hydrogenolysis of C-C single bonds 9107.11 Catalytic oxidations with molecular oxygen 9117.11.1 Heme-dependent monooxygenase oxidations 9127.11.2 Chemical aerobic C-H oxidations 9147.11.3 Reductive activation of molecular oxygen 9177.11.4 Oxidation of alcohols with molecular oxygen 9187.11.5 Wacker process 9207.12 Catalyzed nucleophilic aromatic substitutions 9227.12.1 Ullmann-Goldberg reactions 9237.12.2 Buchwald-Hartwig reactions 926References 9278 Transition-metal-catalyzed C-C bond forming reactions 10298.1 Introduction 10298.2 Organic compounds from carbon monoxide 10308.2.1 Fischer-Tropsch reactions 10308.2.2 Carbonylation of methanol 10328.2.3 Hydroformylation of alkenes 10348.2.4 Silylformylation 10398.2.5 Reppe carbonylations 10418.2.6 Pd(II)-mediated oxidative carbonylations 10428.2.7 Pauson-Khand reaction 10438.2.8 Carbonylation of halides: synthesis of carboxylic derivatives 10478.2.9 Reductive carbonylation of halides: synthesis of carbaldehydes 10498.2.10 Carbonylation of epoxides and aziridines 10508.2.11 Hydroformylation and silylformylation of epoxides 10538.3 Direct hydrocarbation of unsaturated compounds 10538.3.1 Hydroalkylation of alkenes: alkylation of alkanes 10548.3.2 Alder ene-reaction of unactivated alkenes and alkynes 10568.3.3 Hydroarylation of alkenes: alkylation of arenes and heteroarenes 10578.3.4 Hydroarylation of alkynes: alkenylation of arenes and heteroarenes 10608.3.5 Hydroarylation of carbon-heteroatom multiple bonds 10628.3.6 Hydroalkenylation of alkynes, alkenes, and carbonyl compounds 10628.3.7 Hydroacylation of alkenes and alkynes 10638.3.8 Hydrocyanation of alkenes and alkynes 10668.3.9 Direct reductive hydrocarbation of unsaturated compounds 10678.3.10 Direct hydrocarbation via transfer hydrogenation 10698.4 Carbacarbation of unsaturated compounds and cycloadditions 10708.4.1 Formal [?2+?2]-cycloadditions 10728.4.2 (2+1)-Cycloadditions 10728.4.3 Ohloff-Rautenstrauch cyclopropanation 10778.4.4 [?2+?2]-Cycloadditions 10788.4.5 (3+1)-Cycloadditions 10808.4.6 (3+2)-Cycloadditions 10818.4.7 (4+1)-Cycloadditions 10878.4.8 (2+2+1)-Cycloadditions 10898.4.9 [?4+?2]-Cycloadditions of unactivated cycloaddents 10908.4.10 (2+2+2)-Cycloadditions 10968.4.11 (3+3)-Cycloadditions 11018.4.12 (3+2+1)-Cycloadditions 11028.4.13 (4+3)-Cycloadditions 11038.4.14 (5+2)-Cycloadditions 11058.4.15 (4+4)-Cycloadditions 11088.4.16 (4+2+2)-Cycloadditions 11098.4.17 (6+2)-Cycloadditions 11108.4.18 (2+2+2+2)-Cycloadditions 11118.4.19 (5+2+1)-Cycloadditions 11128.4.20 (7+1)-Cycloadditions 11128.4.21 Further examples of high-order catalyzed cycloadditions 11128.4.22 Annulations through catalytic intramolecular hydrometallation 11158.4.23 Oxidative annulations 11158.5 Didehydrogenative C-C-coupling reactions 11168.5.1 Glaser-Hay reaction: oxidative alkyne homocoupling 11168.5.2 Oxidative C-C cross-coupling reactions 11178.5.3 Oxidative aryl/aryl homocoupling reactions 11198.5.4 Oxidative aryl/aryl cross-coupling reactions 11218.5.5 TEMPO-cocatalyzed oxidative C-C coupling reactions 11228.5.6 Oxidative aminoalkylation of alkynes and active C-H moieties 11238.6 Alkane, alkene, and alkyne metathesis 11248.6.1 Alkane metathesis 11258.6.2 Alkene metathesis 11268.6.3 Enyne metathesis: alkene/alkyne cross-metathesis 11318.6.4 Alkyne metathesis 11338.7 Additions of organometallic reagents 11348.7.1 Additions of Grignard reagents 11368.7.2 Additions of alkylzinc reagents 11428.7.3 Additions of organoaluminum compounds 11438.7.4 Additions of organoboron, silicium , and zirconium compounds 11458.8 Displacement reactions 11488.8.1 Kharash cross-coupling and Kumada-Tamao-Corriu reaction 11488.8.2 Negishi cross-coupling 11548.8.3 Stille cross-coupling and carbonylative Stille reaction 11578.8.4 Suzuki-Miyaura cross-coupling 11618.8.5 Hiyama cross-coupling 11668.8.6 Tsuji-Trost reaction: allylic alkylation 11688.8.7 Mizoroki-Heck coupling 11718.8.8 Sonogashira-Hagihara cross-coupling 11798.8.9 Arylation of arenes(heteroarenes) with aryl(heteroaryl) derivatives 11828.8.10 -Arylation of carbonyl compounds and nitriles 11878.8.11 Direct arylation and alkynylation of nonactivated C-H bonds in alkyl groups 11898.8.12 Direct alkylation of nonactivated C-H bonds in alkyl groups 1190References 1191Index 1317