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Organic Chemistry: Theory, Reactivity and Mechanisms in Modern Synthesis

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Organic Chemistry: Theory, Reactivity and Mechanisms in Modern Synthesis

Pierre Vogel, Kendall N. Houk

ISBN: 978-3-527-81927-0 August 2019 1382 Pages

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Provides the background, tools, and models required to understand organic synthesis and plan chemical reactions more efficiently

Knowledge 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. Grubbs


Organic 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 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

1.4.1 Contributions from translation energy levels 5

1.4.2 Contributions from rotational energy levels 5

1.4.3 Contributions from vibrational energy levels 6

1.4.4 Entropy of reaction depends above all on the change of the number of molecules between products and reactants 7

1.4.5 Additions are favored thermodynamically on cooling, fragmentations on heating 7

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

1.6.1 Effect of electronegativity on bond strength 10

1.6.2 Effects of electronegativity and of hyperconjugation 11

1.6.3 π-Conjugation and hyperconjugation in carboxylic functions 12

1.6.4 Degree of chain branching and Markovnikov’s rule 13

1.7 Standard heats of typical organic reactions 14

1.7.1 Standard heats of hydrogenation and hydrocarbation 14

1.7.2 Standard heats of C–H oxidations 15

1.7.3 Relative stabilities of alkyl-substituted ethylenes 17

1.7.4 Effect of fluoro substituents on hydrocarbon stabilities 17

1.7.5 Storage of hydrogen in the form of formic acid 18

1.8 Ionization energies and electron affinities 20

1.9 Homolytic bond dissociations; heats of formation of radicals 22

1.9.1 Measurement of bond dissociation energies 22

1.9.2 Substituent effects on the relative stabilities of radicals 25

1.9.3 π-Conjugation in benzyl, allyl, and propargyl radicals 25

1.10 Heterolytic bond dissociation enthalpies 28

1.10.1 Measurement of gas-phase heterolytic bond dissociation enthalpies 28

1.10.2 Thermochemistry of ions in the gas phase 29

1.10.3 Gas-phase acidities 30

1.11 Electron transfer equilibria 32

1.12 Heats of formation of neutral, transient compounds 32

1.12.1 Measurements of the heats of formation of carbenes 32

1.12.2 Measurements of the heats of formation of diradicals 33

1.12.3 Keto/enol tautomerism 33

1.12.4 Heat of formation of highly reactive cyclobutadiene 36

1.12.5 Estimate of heats of formation of diradicals 36

1.13 Electronegativity and absolute hardness 37

1.14 Chemical conversion and selectivity controlled by thermodynamics 40

1.14.1 Equilibrium shifts (Le Chatelier’s principle in action) 40

1.14.2 Importance of chirality in biology and medicine 41

1.14.3 Resolution of racemates into enantiomers 43

1.14.4 Thermodynamically controlled deracemization 46

1.14.5 Self-disproportionation of enantiomers 48

1.15 Thermodynamic (equilibrium) isotopic effects 49

1.A Appendix, Table 1.A.1 to Table 1.A.24 53

References 92

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

2.5.1 Gauche interactions: the preferred conformations of alkyl chains 114

2.5.2 (E)- vs. (Z)-alkenes and ortho-substitution in benzene derivatives 117

2.6 Ring strain and conformational flexibility of cyclic compounds 117

2.6.1 Cyclopropane and cyclobutane have nearly the same strain energy 118

2.6.2 Cyclopentane is a flexible cycloalkane 119

2.6.3 Conformational analysis of cyclohexane 119

2.6.4 Conformational analysis of cyclohexanones 121

2.6.5 Conformational analysis of cyclohexene 122

2.6.6 Medium-sized cycloalkanes 122

2.6.7 Conformations and ring strain in polycycloalkanes 124

2.6.8 Ring strain in cycloalkenes 125

2.6.9 Bredt’s rule and “anti-Bredt” alkenes 125

2.6.10 Allylic 1,3- and 1,2-strain: the model of banana bonds 126

2.7 𝜋/π-, n/π-, σ/π-, and n/σ-interactions 127

2.7.1 Conjugated dienes and diynes 127

2.7.2 Atropisomerism in 1,3-dienes and diaryl compounds 129

2.7.3 𝛼,β-Unsaturated carbonyl compounds 130

2.7.4 Stabilization by aromaticity 130

2.7.5 Stabilization by n(Z:)/𝜋 conjugation 132

2.7.6 𝜋/π-Conjugation and 𝜎/π-hyperconjugation in esters, thioesters, and amides 133

2.7.7 Oximes are more stable than imines toward hydrolysis 136

2.7.8 Aromatic stabilization energies of heterocyclic compounds 136

2.7.9 Geminal disubstitution: enthalpic anomeric effects 139

2.7.10 Conformational anomeric effect 141

2.8 Other deviations to additivity rules 144

2.9 Major role of translational entropy on equilibria 146

2.9.1 Aldol and crotonalization reactions 146

2.9.2 Aging of wines 148

2.10 Entropy of cyclization: loss of degrees of free rotation 151

2.11 Entropy as a synthetic tool 151

2.11.1 Pyrolysis of esters 151

2.11.2 Method of Chugaev 152

2.11.3 Eschenmoser–Tanabe fragmentation 152

2.11.4 Eschenmoser fragmentation 153

2.11.5 Thermal 1,4-eliminations 153

2.11.6 Retro-Diels–Alder reactions 156

2.A Appendix, Table 2.A.1 to Table 2.A.2 157

References 161

3 Rates of chemical reactions 177

3.1 Introduction 177

3.2 Differential and integrated rate laws 177

3.2.1 Order of reactions 178

3.2.2 Molecularity and reaction mechanisms 179

3.2.3 Examples of zero order reactions 181

3.2.4 Reversible reactions 182

3.2.5 Parallel reactions 183

3.2.6 Consecutive reactions and steady-state approximation 183

3.2.7 Consecutive reactions: maximum yield of the intermediate product 184

3.2.8 Homogeneous catalysis: Michaelis–Menten kinetics 185

3.2.9 Competitive vs. noncompetitive inhibition 186

3.2.10 Heterogeneous catalysis: reactions at surfaces 187

3.3 Activation parameters 188

3.3.1 Temperature effect on the selectivity of two parallel reactions 190

3.3.2 The Curtin–Hammett principle 190

3.4 Relationship between activation entropy and the reaction mechanism 192

3.4.1 Homolysis and radical combination in the gas phase 192

3.4.2 Isomerizations in the gas phase 193

3.4.3 Example of homolysis assisted by bond formation: the Cope rearrangement 195

3.4.4 Example of homolysis assisted by bond-breaking and bond-forming processes: retro–carbonyl–ene reaction 195

3.4.5 Can a reaction be assisted by neighboring groups? 197

3.5 Competition between cyclization and intermolecular condensation 197

3.5.1 Thorpe–Ingold effect 198

3.6 Effect of pressure: activation volume 201

3.6.1 Relationship between activation volume and the mechanism of reaction 201

3.6.2 Detection of change of mechanism 202

3.6.3 Synthetic applications of high pressure 203

3.6.4 Rate enhancement by compression of reactants along the reaction coordinates 204

3.6.5 Structural effects on the rate of the Bergman rearrangement 205

3.7 Asymmetric organic synthesis 206

3.7.1 Kinetic resolution 206

3.7.2 Parallel kinetic resolution 211

3.7.3 Dynamic kinetic resolution: kinetic deracemization 212

3.7.4 Synthesis starting from enantiomerically pure natural compounds 215

3.7.5 Use of recoverable chiral auxiliaries 217

3.7.6 Catalytic desymmetrization of achiral compounds 220

3.7.7 Nonlinear effects in asymmetric synthesis 226

3.7.8 Asymmetric autocatalysis 228

3.8 Chemo- and site-selective reactions 229

3.9 Kinetic isotope effects and reaction mechanisms 231

3.9.1 Primary kinetic isotope effects: the case of hydrogen transfers 231

3.9.2 Tunneling effects 232

3.9.3 Nucleophilic substitution and elimination reactions 234

3.9.4 Steric effect on kinetic isotope effects 239

3.9.5 Simultaneous determination of multiple small kinetic isotope effects at natural abundance 239

References 240

4 Molecular orbital theories 271

4.1 Introduction 271

4.2 Background of quantum chemistry 271

4.3 Schrödinger equation 272

4.4 Coulson and Longuet-Higgins approach 274

4.4.1 Hydrogen molecule 275

4.4.2 Hydrogenoid molecules: The PMO theory 276

4.5 Hückel method 277

4.5.1 π-Molecular orbitals of ethylene 278

4.5.2 Allyl cation, radical, and anion 279

4.5.3 Shape of allyl π-molecular orbitals 282

4.5.4 Cyclopropenyl systems 282

4.5.5 Butadiene 285

4.5.6 Cyclobutadiene and its electronic destabilization (antiaromaticity) 286

4.5.7 Geometries of cyclobutadienes, singlet and triplet states 288

4.5.8 Pentadienyl and cyclopentadienyl systems 291

4.5.9 Cyclopentadienyl anion and bishomocyclopentadienyl anions 292

4.5.10 Benzene and its aromatic stabilization energy 294

4.5.11 3,4-Dimethylidenecyclobutene is not stabilized by π-conjugation 295

4.5.12 Fulvene 297

4.5.13 [N]Annulenes 298

4.5.14 Cyclooctatetraene 301

4.5.15 π-systems with heteroatoms 302

4.6 Aromatic stabilization energy of heterocyclic compounds 305

4.7 Homoconjugation 308

4.7.1 Homoaromaticity in cyclobutenyl cation 308

4.7.2 Homoaromaticity in homotropylium cation 308

4.7.3 Homoaromaticity in cycloheptatriene 310

4.7.4 Bishomoaromaticity in bishomotropylium ions 311

4.7.5 Bishomoaromaticity in neutral semibullvalene derivatives 312

4.7.6 Barrelene effect 313

4.8 Hyperconjugation 314

4.8.1 Neutral, positive, and negative hyperconjugation 314

4.8.2 Hyperconjugation in cyclopentadienes 315

4.8.3 Nonplanarity of bicyclo[2.2.1]hept-2-ene double bond 315

4.8.4 Conformation of unsaturated and saturated systems 317

4.8.5 Hyperconjugation in radicals 319

4.8.6 Hyperconjugation in carbenium ions 320

4.8.7 Hyperconjugation in carbanions 320

4.8.8 Cyclopropyl vs. cyclobutyl substituent effect 322

4.9 Heilbronner Möbius aromatic [N]annulenes 324

4.10 Conclusion 326

References 326

5 Pericyclic reactions 339

5.1 Introduction 339

5.2 Electrocyclic reactions 340

5.2.1 Stereochemistry of thermal cyclobutene-butadiene isomerization: four-electron electrocyclic reactions 340

5.2.2 Longuet-Higgins correlation of electronic configurations 342

5.2.3 Woodward–Hoffmann simplification 345

5.2.4 Aromaticity of transition states in cyclobutene/butadiene electrocyclizations 346

5.2.5 Torquoselectivity of cyclobutene electrocyclic reactions 347

5.2.6 Nazarov cyclizations 350

5.2.7 Thermal openings of three-membered ring systems 354

5.2.8 Six-electron electrocyclic reactions 357

5.2.9 Eight-electron electrocyclic reactions 360

5.3 Cycloadditions and cycloreversions 361

5.3.1 Stereoselectivity of thermal [𝜋2+𝜋2]-cycloadditions: Longuet-Higgins model 362

5.3.2 Woodward–Hoffmann rules for cycloadditions 364

5.3.3 Aromaticity of cycloaddition transition structures 366

5.3.4 Mechanism of thermal [𝜋2+𝜋2]-cycloadditions and [𝜎2+𝜎2]-cycloreversions: 1,4- diradical/zwitterion intermediates or diradicaloid transition structures 368

5.3.5 Cycloadditions of allenes 372

5.3.6 Cycloadditions of ketenes and keteniminium salts 373

5.3.7 Wittig olefination 380

5.3.8 Olefinations analogous to the Wittig reaction 384

5.3.9 Diels–Alder reaction: concerted and non-concerted mechanisms compete 387

5.3.10 Concerted Diels–Alder reactions with synchronous or asynchronous transition states 391

5.3.11 Diradicaloid model for transition states of concerted Diels–Alder reactions 392

5.3.12 Structural effects on the Diels–Alder reactivity 397

5.3.13 Regioselectivity of Diels–Alder reactions 399

5.3.14 Stereoselectivity of Diels–Alder reactions: the Alder “endo rule” 406

5.3.15 π-Facial selectivity of Diels–Alder reactions 408

5.3.16 Examples of hetero-Diels–Alder reactions 411

5.3.17 1,3-Dipolar cycloadditions 420

5.3.18 Sharpless asymmetric dihydroxylation of alkenes 428

5.3.19 Thermal (2+2+2)-cycloadditions 428

5.3.20 Noncatalyzed (4+3)- and (5+2)-cycloadditions 431

5.3.21 Thermal higher order (m+n)-cycloadditions 434

5.4 Cheletropic reactions 437

5.4.1 Cyclopropanation by (2+1)-cheletropic reaction of carbenes 437

5.4.2 Aziridination by (2+1)-cheletropic addition of nitrenes 440

5.4.3 Decarbonylation of cyclic ketones by cheletropic elimination 442

5.4.4 Cheletropic reactions of sulfur dioxide 444

5.4.5 Cheletropic reactions of heavier congeners of carbenes and nitrenes 447

5.5 Thermal sigmatropic rearrangements 451

5.5.1 (1,2)-Sigmatropic rearrangement of carbenium ions 451

5.5.2 (1,2)-Sigmatropic rearrangements of radicals 456

5.5.3 (1,2)-Sigmatropic rearrangements of organoalkali compounds 459

5.5.4 (1,3)-Sigmatropic rearrangements 462

5.5.5 (1,4)-Sigmatropic rearrangements 465

5.5.6 (1,5)-Sigmatropic rearrangements 467

5.5.7 (1,7)-Sigmatropic rearrangements 469

5.5.8 (2,3)-Sigmatropic rearrangements 470

5.5.9 (3,3)-Sigmatropic rearrangements 476

5.5.9.1 Fischer indole synthesis (3,4-diaza-Cope rearrangement) 476

5.5.9.2 Claisen rearrangement and its variants (3-oxa-Cope rearrangements) 476

5.5.9.3 Aza-Claisen rearrangements (3-aza-Cope rearrangements) 481

5.5.9.4 Overman rearrangement (1-oxa-3-aza-Cope rearrangement) 483

5.5.9.5 Thia-Claisen rearrangement (3-thia-Cope rearrangement) 484

5.5.9.6 Cope rearrangements 484

5.5.9.7 Facile anionic oxy-Cope rearrangements 489

5.5.9.8 Acetylenic Cope rearrangements 491

5.5.9.9 Other hetero-Cope rearrangements 492

5.6 Dyotropic rearrangements and transfers 495

5.6.1 Type I dyotropic rearrangements 496

5.6.2 Alkene and alkyne reductions with diimide 498

5.6.3 Type II dyotropic rearrangements 499

5.7 Ene-reactions and related reactions 500

5.7.1 Thermal Alder ene-reactions 501

5.7.2 Carbonyl ene-reactions 504

5.7.3 Other hetero-ene reactions involving hydrogen transfers 504

5.7.4 Metallo-ene-reactions 508

5.7.5 Carbonyl allylation with allylmetals: carbonyl metallo-ene-reactions 509

5.7.6 Aldol reaction 514

5.7.7 Reactions of metal enolates with carbonyl compounds 518

References 526

6 Organic photochemistry 615

6.1 Introduction 615

6.2 Photophysical processes of organic compounds 615

6.2.1 UV–visible spectroscopy: electronic transitions 616

6.2.2 Fluorescence and phosphorescence: singlet and triplet excited states 620

6.2.3 Bimolecular photophysical processes 623

6.3 Unimolecular photochemical reactions of unsaturated hydrocarbons 626

6.3.1 Photoinduced (E)/(Z)-isomerization of alkenes 626

6.3.2 Photochemistry of cyclopropenes, allenes, and alkynes 630

6.3.3 Electrocyclic ring closures of conjugated dienes and ring opening of cyclobutenes 631

6.3.4 The di-π-methane (Zimmerman) rearrangement of 1,4-dienes 633

6.3.5 Electrocyclic interconversions of cyclohexa-1,3-dienes and hexa-1,3,5-trienes 635

6.4 Unimolecular photochemical reactions of carbonyl compounds 637

6.4.1 Norrish type I reaction (α-cleavage) 637

6.4.2 Norrish type II reaction and other intramolecular hydrogen transfers 639

6.4.3 Unimolecular photochemistry of enones and dienones 642

6.5 Unimolecular photoreactions of benzene and heteroaromatic analogs 644

6.5.1 Photoisomerization of benzene 644

6.5.2 Photoisomerizations of pyridines, pyridinium salts, and diazines 646

6.5.3 Photolysis of five-membered ring heteroaromatic compounds 647

6.6 Photocleavage of carbon–heteroatom bonds 649

6.6.1 Photo-Fries, photo-Claisen, and related rearrangements 649

6.6.2 Photolysis of 1,2-diazenes, 3H-diazirines, and diazo compounds 651

6.6.3 Photolysis of alkyl halides 654

6.6.4 Solution photochemistry of aryl and alkenyl halides 657

6.6.5 Photolysis of phenyliodonium salts: formation of aryl and alkenyl cation intermediates 659

6.6.6 Photolytic decomposition of arenediazonium salts in solution 660

6.7 Photocleavage of nitrogen—nitrogen bonds 661

6.7.1 Photolysis of azides 662

6.7.2 Photo-Curtius rearrangement 664

6.7.3 Photolysis of geminal diazides 665

6.7.4 Photolysis of 1,2,3-triazoles and of tetrazoles 666

6.8 Photochemical cycloadditions of unsaturated compounds 667

6.8.1 Photochemical intramolecular (2+2)-cycloadditions of alkenes 668

6.8.2 Photochemical intermolecular (2+2)-cycloadditions of alkenes 672

6.8.3 Photochemical intermolecular (4+2)-cycloadditions of dienes and alkenes 676

6.8.4 Photochemical cycloadditions of benzene and derivatives to alkenes 677

6.8.5 Photochemical cycloadditions of carbonyl compounds 681

6.8.6 Photochemical cycloadditions of imines and related C=N double-bonded compounds 686

6.9 Photo-oxygenation 688

6.9.1 Reactions of ground-state molecular oxygen with hydrocarbons 688

6.9.2 Singlet molecular oxygen 691

6.9.3 Diels–Alder reactions of singlet oxygen 695

6.9.4 Dioxa-ene reactions of singlet oxygen 700

6.9.5 (2+2)-Cycloadditions of singlet oxygen 704

6.9.6 1,3-Dipolar cycloadditions of singlet oxygen 705

6.9.7 Nonpericyclic reactions of singlet oxygen 707

6.10 Photoinduced electron transfers 710

6.10.1 Marcus model 711

6.10.2 Catalysis through photoreduction 711

6.10.3 Photoinduced net reductions 715

6.10.4 Catalysis through photo-oxidation 717

6.10.5 Photoinduced net oxidations 721

6.10.6 Generation of radical intermediates by PET 724

6.10.7 Dye-sensitized solar cells 726

6.11 Chemiluminescence and bioluminescence 727

6.11.1 Thermal isomerization of Dewar benzene into benzene 728

6.11.2 Oxygenation of electron-rich organic compounds 729

6.11.3 Thermal fragmentation of 1,2-dioxetanes 732

6.11.4 Peroxylate chemiluminescence 734

6.11.5 Firefly bioluminescence 734

References 735

7 Catalytic reactions 795

7.1 Introduction 795

7.2 Acyl group transfers 798

7.2.1 Esterification and ester hydrolysis 798

7.2.2 Acid or base-catalyzed acyl transfers 799

7.2.3 Amphoteric compounds are good catalysts for acyl transfers 802

7.2.4 Catalysis by nucleofugal group substitution 802

7.2.5 N-heterocyclic carbene-catalyzed transesterifications 804

7.2.6 Enzyme-catalyzed acyl transfers 806

7.2.7 Mimics of carboxypeptidase A 807

7.2.8 Direct amide bond formation from amines and carboxylic acids 807

7.3 Catalysis of nucleophilic additions 810

7.3.1 Catalysis of nucleophilic additions to aldehydes, ketones and imines 810

7.3.2 Bifunctional catalysts for nucleophilic addition/elimination 811

7.3.3 σ- and π-Nucleophiles as catalysts for nucleophilic additions to aldehydes and ketones 812

7.3.4 Catalysis by self-assembled encapsulation 813

7.3.5 Catalysis of 1,4-additions (conjugate additions) 814

7.4 Anionic nucleophilic displacement reactions 815

7.4.1 Pulling on the leaving group 815

7.4.2 Phase transfer catalysis 816

7.5 Catalytical Umpolung C—C bond forming reactions 818

7.5.1 Benzoin condensation: Umpolung of aldehydes 819

7.5.2 Stetter reaction: Umpolung of aldehydes 821

7.5.3 Umpolung of enals 822

7.5.4 Umpolung of Michael acceptors 823

7.5.5 Rauhut–Currier reaction 826

7.5.6 Morita–Baylis–Hillman reaction 826

7.5.7 Nucleophilic catalysis of cycloadditions 828

7.5.8 Catalysis through electron-transfer: hole-catalyzed reactions 831

7.5.9 Umpolung of enamines 834

7.5.10 Catalysis through electron-transfer: Umpolung through electron capture 836

7.6 Brønsted and Lewis acids as catalysts in C—C bond forming reactions 836

7.6.1 Mukaiyama aldol reactions 839

7.6.2 Metallo-carbonyl-ene reactions 843

7.6.3 Carbonyl-ene reactions 846

7.6.4 Imine-ene reactions 847

7.6.5 Alder-ene reaction 848

7.6.6 Diels–Alder reaction 849

7.6.7 Brønsted and Lewis acid-catalyzed hetero-Diels-Alder reactions 851

7.6.8 Acid-catalyzed (2+2)-cycloadditions 853

7.6.9 Lewis acid catalyzed (3+2)- and (3+3)-cycloadditions 855

7.6.10 Lewis acid promoted (5+2)-cycloadditions 857

7.7 Bonding in transition metal complexes and their reactions 858

7.7.1 The π-complex theory 858

7.7.2 The isolobal formalism 860

7.7.3 σ-Complexes of dihydrogen 863

7.7.4 σ-Complexes of C—H bonds and agostic bonding 866

7.7.5 σ-Complexes of C—C bonds and C—C bond activation 867

7.7.6 Reactions of transition metal complexes are modeled by reactions of organic chemistry 869

7.7.7 Ligand exchange reactions 869

7.7.8 Oxidative additions and reductive eliminations 873

7.7.9 α-Insertions/α-eliminations 880

7.7.10 β-Insertions/β-eliminations 883

7.7.11 α-Cycloinsertions/α-cycloeliminations: metallacyclobutanes, metallacyclobutenes 886

7.7.12 Metallacyclobutenes: alkyne polymerization, enyne metathesis, cyclopentadiene synthesis 887

7.7.13 Metallacyclobutadiene: alkyne metathesis 889

7.7.14 Matallacyclopentanes, metallacyclopentenes, metallacyclopentadienes: oxidative cyclizations

(β-cycloinsertions) and reductive fragmentations (β-cycloeliminations) 890

7.8 Catalytic hydrogenation 891

7.8.1 Heterogeneous catalysts for alkene, alkyne, and arene hydrogenation 892

7.8.2 Homogeneous catalysts for alkene and alkyne hydrogenation 894

7.8.3 Dehydrogenation of alkanes 897

7.8.4 Hydrogenation of alkynes into alkenes 897

7.8.5 Catalytic hydrogenation of arenes and heteroarenes 899

7.8.6 Catalytic hydrogenation of ketones and aldehydes 899

7.8.7 Catalytic hydrogenation of carboxylic acids, their esters and amides 902

7.8.8 Hydrogenation of carbon dioxide 903

7.8.9 Catalytic hydrogenation of nitriles and imines 904

7.8.10 Catalytic hydrogenolysis of C–halogen and C–chalcogen bonds 906

7.9 Catalytic reactions of silanes 906

7.9.1 Reduction of alkyl halides 906

7.9.2 Reduction of carbonyl compounds 907

7.9.3 Alkene hydrosilylation 909

7.10 Hydrogenolysis of C—C single bonds 910

7.11 Catalytic oxidations with molecular oxygen 911

7.11.1 Heme-dependent monooxygenase oxidations 912

7.11.2 Chemical aerobic C—H oxidations 914

7.11.3 Reductive activation of molecular oxygen 917

7.11.4 Oxidation of alcohols with molecular oxygen 918

7.11.5 Wacker process 920

7.12 Catalyzed nucleophilic aromatic substitutions 922

7.12.1 Ullmann–Goldberg reactions 923

7.12.2 Buchwald–Hartwig reactions 926

References 927

8 Transition-metal-catalyzed C—C bond forming reactions 1029

8.1 Introduction 1029

8.2 Organic compounds from carbon monoxide 1030

8.2.1 Fischer–Tropsch reactions 1030

8.2.2 Carbonylation of methanol 1032

8.2.3 Hydroformylation of alkenes 1034

8.2.4 Silylformylation 1039

8.2.5 Reppe carbonylations 1041

8.2.6 Pd(II)-mediated oxidative carbonylations 1042

8.2.7 Pauson–Khand reaction 1043

8.2.8 Carbonylation of halides: synthesis of carboxylic derivatives 1047

8.2.9 Reductive carbonylation of halides: synthesis of carbaldehydes 1049

8.2.10 Carbonylation of epoxides and aziridines 1050

8.2.11 Hydroformylation and silylformylation of epoxides 1053

8.3 Direct hydrocarbation of unsaturated compounds 1053

8.3.1 Hydroalkylation of alkenes: alkylation of alkanes 1054

8.3.2 Alder ene-reaction of unactivated alkenes and alkynes 1056

8.3.3 Hydroarylation of alkenes: alkylation of arenes and heteroarenes 1057

8.3.4 Hydroarylation of alkynes: alkenylation of arenes and heteroarenes 1060

8.3.5 Hydroarylation of carbon-heteroatom multiple bonds 1062

8.3.6 Hydroalkenylation of alkynes, alkenes, and carbonyl compounds 1062

8.3.7 Hydroacylation of alkenes and alkynes 1063

8.3.8 Hydrocyanation of alkenes and alkynes 1066

8.3.9 Direct reductive hydrocarbation of unsaturated compounds 1067

8.3.10 Direct hydrocarbation via transfer hydrogenation 1069

8.4 Carbacarbation of unsaturated compounds and cycloadditions 1070

8.4.1 Formal [𝜎2+𝜋2]-cycloadditions 1072

8.4.2 (2+1)-Cycloadditions 1072

8.4.3 Ohloff–Rautenstrauch cyclopropanation 1077

8.4.4 [𝜋2+𝜋2]-Cycloadditions 1078

8.4.5 (3+1)-Cycloadditions 1080

8.4.6 (3+2)-Cycloadditions 1081

8.4.7 (4+1)-Cycloadditions 1087

8.4.8 (2+2+1)-Cycloadditions 1089

8.4.9 [𝜋4+𝜋2]-Cycloadditions of unactivated cycloaddents 1090

8.4.10 (2+2+2)-Cycloadditions 1096

8.4.11 (3+3)-Cycloadditions 1101

8.4.12 (3+2+1)-Cycloadditions 1102

8.4.13 (4+3)-Cycloadditions 1103

8.4.14 (5+2)-Cycloadditions 1105

8.4.15 (4+4)-Cycloadditions 1108

8.4.16 (4+2+2)-Cycloadditions 1109

8.4.17 (6+2)-Cycloadditions 1110

8.4.18 (2+2+2+2)-Cycloadditions 1111

8.4.19 (5+2+1)-Cycloadditions 1112

8.4.20 (7+1)-Cycloadditions 1112

8.4.21 Further examples of high-order catalyzed cycloadditions 1112

8.4.22 Annulations through catalytic intramolecular hydrometallation 1115

8.4.23 Oxidative annulations 1115

8.5 Didehydrogenative C—C-coupling reactions 1116

8.5.1 Glaser–Hay reaction: oxidative alkyne homocoupling 1116

8.5.2 Oxidative C—C cross-coupling reactions 1117

8.5.3 Oxidative aryl/aryl homocoupling reactions 1119

8.5.4 Oxidative aryl/aryl cross-coupling reactions 1121

8.5.5 TEMPO-cocatalyzed oxidative C—C coupling reactions 1122

8.5.6 Oxidative aminoalkylation of alkynes and active C—H moieties 1123

8.6 Alkane, alkene, and alkyne metathesis 1124

8.6.1 Alkane metathesis 1125

8.6.2 Alkene metathesis 1126

8.6.3 Enyne metathesis: alkene/alkyne cross-metathesis 1131

8.6.4 Alkyne metathesis 1133

8.7 Additions of organometallic reagents 1134

8.7.1 Additions of Grignard reagents 1136

8.7.2 Additions of alkylzinc reagents 1142

8.7.3 Additions of organoaluminum compounds 1143

8.7.4 Additions of organoboron, silicium , and zirconium compounds 1145

8.8 Displacement reactions 1148

8.8.1 Kharash cross-coupling and Kumada–Tamao–Corriu reaction 1148

8.8.2 Negishi cross-coupling 1154

8.8.3 Stille cross-coupling and carbonylative Stille reaction 1157

8.8.4 Suzuki–Miyaura cross-coupling 1161

8.8.5 Hiyama cross-coupling 1166

8.8.6 Tsuji–Trost reaction: allylic alkylation 1168

8.8.7 Mizoroki–Heck coupling 1171

8.8.8 Sonogashira–Hagihara cross-coupling 1179

8.8.9 Arylation of arenes(heteroarenes) with aryl(heteroaryl) derivatives 1182

8.8.10 α-Arylation of carbonyl compounds and nitriles 1187

8.8.11 Direct arylation and alkynylation of nonactivated C—H bonds in alkyl groups 1189

8.8.12 Direct alkylation of nonactivated C—H bonds in alkyl groups 1190

References 1191

Index 1317