Organic Chemistry - Theory, Reactivity and Mechanisms in Modern Synthesis
von: Pierre Vogel, Kendall N. Houk
Wiley-VCH, 2019
ISBN: 9783527819256
Sprache: Englisch
1382 Seiten, Download: 119767 KB
Format: Online-Lesen, PDF
geeignet für:
Cover | 1 | ||
Title Page | 5 | ||
Copyright | 6 | ||
Contents | 7 | ||
Preface | 17 | ||
Foreword | 31 | ||
Chapter 1 Equilibria and thermochemistry | 33 | ||
1.1 Introduction | 33 | ||
1.2 Equilibrium?free enthalpy: reaction?free energy or Gibbs energy | 33 | ||
1.3 Heat of reaction and variation of the entropy of reaction (reaction entropy) | 34 | ||
1.4 Statistical thermodynamics | 36 | ||
1.4.1 Contributions from translation energy levels | 37 | ||
1.4.2 Contributions from rotational energy levels | 37 | ||
1.4.3 Contributions from vibrational energy levels | 38 | ||
1.4.4 Entropy of reaction depends above all on the change of the number of molecules between products and reactants | 39 | ||
1.4.5 Additions are favored thermodynamically on cooling, fragmentations on heating | 39 | ||
1.5 Standard heats of formation | 40 | ||
1.6 What do standard heats of formation tell us about chemical bonding and ground?state properties of organic compounds? | 41 | ||
1.6.1 Effect of electronegativity on bond strength | 42 | ||
1.6.2 Effects of electronegativity and of hyperconjugation | 43 | ||
1.6.3 ??Conjugation and hyperconjugation in carboxylic functions | 44 | ||
1.6.4 Degree of chain branching and Markovnikov's rule | 45 | ||
1.7 Standard heats of typical organic reactions | 46 | ||
1.7.1 Standard heats of hydrogenation and hydrocarbation | 46 | ||
1.7.2 Standard heats of C–H oxidations | 47 | ||
1.7.3 Relative stabilities of alkyl?substituted ethylenes | 49 | ||
1.7.4 Effect of fluoro substituents on hydrocarbon stabilities | 49 | ||
1.7.5 Storage of hydrogen in the form of formic acid | 50 | ||
1.8 Ionization energies and electron affinities | 52 | ||
1.9 Homolytic bond dissociations | 54 | ||
1.9.1 Measurement of bond dissociation energies | 54 | ||
1.9.2 Substituent effects on the relative stabilities of radicals | 57 | ||
1.9.3 ??Conjugation in benzyl, allyl, and propargyl radicals | 57 | ||
1.10 Heterolytic bond dissociation enthalpies | 60 | ||
1.10.1 Measurement of gas?phase heterolytic bond dissociation enthalpies | 60 | ||
1.10.2 Thermochemistry of ions in the gas phase | 61 | ||
1.10.3 Gas?phase acidities | 62 | ||
1.11 Electron transfer equilibria | 64 | ||
1.12 Heats of formation of neutral, transient compounds | 64 | ||
1.12.1 Measurements of the heats of formation of carbenes | 64 | ||
1.12.2 Measurements of the heats of formation of diradicals | 65 | ||
1.12.3 Keto/enol tautomerism | 65 | ||
1.12.4 Heat of formation of highly reactive cyclobutadiene | 68 | ||
1.12.5 Estimate of heats of formation of diradicals | 68 | ||
1.13 Electronegativity and absolute hardness | 69 | ||
1.14 Chemical conversion and selectivity controlled by thermodynamics | 72 | ||
1.14.1 Equilibrium shifts (Le Chatelier's principle in action) | 72 | ||
1.14.2 Importance of chirality in biology and medicine | 73 | ||
1.14.3 Resolution of racemates into enantiomers | 75 | ||
1.14.4 Thermodynamically controlled deracemization | 78 | ||
1.14.5 Self?disproportionation of enantiomers | 80 | ||
1.15 Thermodynamic (equilibrium) isotopic effects | 81 | ||
1.A Appendix, Table 1.A.1 to Table 1.A.24 | 85 | ||
References | 124 | ||
Chapter 2 Additivity rules for thermodynamic parameters and deviations | 141 | ||
2.1 Introduction | 141 | ||
2.2 Molecular groups | 142 | ||
2.3 Determination of the standard group equivalents (group equivalents) | 143 | ||
2.4 Determination of standard entropy increments | 145 | ||
2.5 Steric effects | 146 | ||
2.5.1 Gauche interactions: the preferred conformations of alkyl chains | 146 | ||
2.5.2 (E)? vs. (Z)?alkenes and ortho?substitution in benzene derivatives | 149 | ||
2.6 Ring strain and conformational flexibility of cyclic compounds | 149 | ||
2.6.1 Cyclopropane and cyclobutane have nearly the same strain energy | 150 | ||
2.6.2 Cyclopentane is a flexible cycloalkane | 151 | ||
2.6.3 Conformational analysis of cyclohexane | 151 | ||
2.6.4 Conformational analysis of cyclohexanones | 153 | ||
2.6.5 Conformational analysis of cyclohexene | 154 | ||
2.6.6 Medium?sized cycloalkanes | 154 | ||
2.6.7 Conformations and ring strain in polycycloalkanes | 156 | ||
2.6.8 Ring strain in cycloalkenes | 157 | ||
2.6.9 Bredt's rule and “anti?Bredt” alkenes | 157 | ||
2.6.10 Allylic 1,3? and 1,2?strain: the model of banana bonds | 158 | ||
2.7 ?/??, n/??, ?/??, and n/??interactions | 159 | ||
2.7.1 Conjugated dienes and diynes | 159 | ||
2.7.2 Atropisomerism in 1,3?dienes and diaryl compounds | 161 | ||
2.7.3 ?,??Unsaturated carbonyl compounds | 162 | ||
2.7.4 Stabilization by aromaticity | 162 | ||
2.7.5 Stabilization by n(Z:)/? conjugation | 164 | ||
2.7.6 ?/??Conjugation and ?/??hyperconjugation in esters, thioesters, and amides | 165 | ||
2.7.7 Oximes are more stable than imines toward hydrolysis | 168 | ||
2.7.8 Aromatic stabilization energies of heterocyclic compounds | 168 | ||
2.7.9 Geminal disubstitution: enthalpic anomeric effects | 171 | ||
2.7.10 Conformational anomeric effect | 173 | ||
2.8 Other deviations to additivity rules | 176 | ||
2.9 Major role of translational entropy on equilibria | 178 | ||
2.9.1 Aldol and crotonalization reactions | 178 | ||
2.9.2 Aging of wines | 180 | ||
2.10 Entropy of cyclization: loss of degrees of free rotation | 183 | ||
2.11 Entropy as a synthetic tool | 183 | ||
2.11.1 Pyrolysis of esters | 183 | ||
2.11.2 Method of Chugaev | 184 | ||
2.11.3 Eschenmoser–Tanabe fragmentation | 184 | ||
2.11.4 Eschenmoser fragmentation | 185 | ||
2.11.5 Thermal 1,4?eliminations | 185 | ||
2.11.6 Retro?Diels–Alder reactions | 188 | ||
2.A Appendix, Table 2.A.1 to Table 2.A.2 | 189 | ||
References | 193 | ||
Chapter 3 Rates of chemical reactions | 209 | ||
3.1 Introduction | 209 | ||
3.2 Differential and integrated rate laws | 209 | ||
3.2.1 Order of reactions | 210 | ||
3.2.2 Molecularity and reaction mechanisms | 211 | ||
3.2.3 Examples of zero order reactions | 213 | ||
3.2.4 Reversible reactions | 214 | ||
3.2.5 Parallel reactions | 215 | ||
3.2.6 Consecutive reactions and steady?state approximation | 215 | ||
3.2.7 Consecutive reactions: maximum yield of the intermediate product | 216 | ||
3.2.8 Homogeneous catalysis: Michaelis–Menten kinetics | 217 | ||
3.2.9 Competitive vs. noncompetitive inhibition | 218 | ||
3.2.10 Heterogeneous catalysis: reactions at surfaces | 219 | ||
3.3 Activation parameters | 220 | ||
3.3.1 Temperature effect on the selectivity of two parallel reactions | 222 | ||
3.3.2 The Curtin–Hammett principle | 222 | ||
3.4 Relationship between activation entropy and the reaction mechanism | 224 | ||
3.4.1 Homolysis and radical combination in the gas phase | 224 | ||
3.4.2 Isomerizations in the gas phase | 225 | ||
3.4.3 Example of homolysis assisted by bond formation: the Cope rearrangement | 227 | ||
3.4.4 Example of homolysis assisted by bond?breaking and bond?forming processes: retro–carbonyl–ene reaction | 227 | ||
3.4.5 Can a reaction be assisted by neighboring groups? | 229 | ||
3.5 Competition between cyclization and intermolecular condensation | 229 | ||
3.5.1 Thorpe–Ingold effect | 230 | ||
3.6 Effect of pressure: activation volume | 233 | ||
3.6.1 Relationship between activation volume and the mechanism of reaction | 233 | ||
3.6.2 Detection of change of mechanism | 234 | ||
3.6.3 Synthetic applications of high pressure | 235 | ||
3.6.4 Rate enhancement by compression of reactants along the reaction coordinates | 236 | ||
3.6.5 Structural effects on the rate of the Bergman rearrangement | 237 | ||
3.7 Asymmetric organic synthesis | 238 | ||
3.7.1 Kinetic resolution | 238 | ||
3.7.2 Parallel kinetic resolution | 243 | ||
3.7.3 Dynamic kinetic resolution: kinetic deracemization | 244 | ||
3.7.4 Synthesis starting from enantiomerically pure natural compounds | 247 | ||
3.7.5 Use of recoverable chiral auxiliaries | 249 | ||
3.7.6 Catalytic desymmetrization of achiral compounds | 252 | ||
3.7.7 Nonlinear effects in asymmetric synthesis | 258 | ||
3.7.8 Asymmetric autocatalysis | 260 | ||
3.8 Chemo? and site?selective reactions | 261 | ||
3.9 Kinetic isotope effects and reaction mechanisms | 263 | ||
3.9.1 Primary kinetic isotope effects: the case of hydrogen transfers | 263 | ||
3.9.2 Tunneling effects | 264 | ||
3.9.3 Nucleophilic substitution and elimination reactions | 266 | ||
3.9.4 Steric effect on kinetic isotope effects | 271 | ||
3.9.5 Simultaneous determination of multiple small kinetic isotope effects at natural abundance | 271 | ||
References | 272 | ||
Chapter 4 Molecular orbital theories | 303 | ||
4.1 Introduction | 303 | ||
4.2 Background of quantum chemistry | 303 | ||
4.3 Schrödinger equation | 304 | ||
4.4 Coulson and Longuet?Higgins approach | 306 | ||
4.4.1 Hydrogen molecule | 307 | ||
4.4.2 Hydrogenoid molecules: The PMO theory | 308 | ||
4.5 Hückel method | 309 | ||
4.5.1 ??Molecular orbitals of ethylene | 310 | ||
4.5.2 Allyl cation, radical, and anion | 311 | ||
4.5.3 Shape of allyl ??molecular orbitals | 314 | ||
4.5.4 Cyclopropenyl systems | 314 | ||
4.5.5 Butadiene | 317 | ||
4.5.6 Cyclobutadiene and its electronic destabilization (antiaromaticity) | 318 | ||
4.5.7 Geometries of cyclobutadienes, singlet and triplet states | 320 | ||
4.5.8 Pentadienyl and cyclopentadienyl systems | 323 | ||
4.5.9 Cyclopentadienyl anion and bishomocyclopentadienyl anions | 324 | ||
4.5.10 Benzene and its aromatic stabilization energy | 326 | ||
4.5.11 3,4?Dimethylidenecyclobutene is not stabilized by ??conjugation | 327 | ||
4.5.12 Fulvene | 329 | ||
4.5.13 [N]Annulenes | 330 | ||
4.5.14 Cyclooctatetraene | 333 | ||
4.5.15 ??Systems with heteroatoms | 334 | ||
4.6 Aromatic stabilization energy of heterocyclic compounds | 337 | ||
4.7 Homoconjugation | 340 | ||
4.7.1 Homoaromaticity in cyclobutenyl cation | 340 | ||
4.7.2 Homoaromaticity in homotropylium cation | 340 | ||
4.7.3 Homoaromaticity in cycloheptatriene | 342 | ||
4.7.4 Bishomoaromaticity in bishomotropylium ions | 343 | ||
4.7.5 Bishomoaromaticity in neutral semibullvalene derivatives | 344 | ||
4.7.6 Barrelene effect | 345 | ||
4.8 Hyperconjugation | 346 | ||
4.8.1 Neutral, positive, and negative hyperconjugation | 346 | ||
4.8.2 Hyperconjugation in cyclopentadienes | 347 | ||
4.8.3 Nonplanarity of bicyclo[2.2.1]hept?2?ene double bond | 347 | ||
4.8.4 Conformation of unsaturated and saturated systems | 349 | ||
4.8.5 Hyperconjugation in radicals | 351 | ||
4.8.6 Hyperconjugation in carbenium ions | 352 | ||
4.8.7 Hyperconjugation in carbanions | 352 | ||
4.8.8 Cyclopropyl vs. cyclobutyl substituent effect | 354 | ||
4.9 Heilbronner möbius aromatic [N]annulenes | 356 | ||
4.10 Conclusion | 358 | ||
References | 358 | ||
Chapter 5 Pericyclic reactions | 371 | ||
5.1 Introduction | 371 | ||
5.2 Electrocyclic reactions | 372 | ||
5.2.1 Stereochemistry of thermal cyclobutene?butadiene isomerization: four?electron electrocyclic reactions | 372 | ||
5.2.2 Longuet?Higgins correlation of electronic configurations | 374 | ||
5.2.3 Woodward–Hoffmann simplification | 377 | ||
5.2.4 Aromaticity of transition states in cyclobutene/butadiene electrocyclizations | 378 | ||
5.2.5 Torquoselectivity of cyclobutene electrocyclic reactions | 379 | ||
5.2.6 Nazarov cyclizations | 382 | ||
5.2.7 Thermal openings of three?membered ring systems | 386 | ||
5.2.8 Six?electron electrocyclic reactions | 389 | ||
5.2.9 Eight?electron electrocyclic reactions | 392 | ||
5.3 Cycloadditions and cycloreversions | 393 | ||
5.3.1 Stereoselectivity of thermal [?2+?2]?cycloadditions: Longuet?Higgins model | 394 | ||
5.3.2 Woodward–Hoffmann rules for cycloadditions | 396 | ||
5.3.3 Aromaticity of cycloaddition transition structures | 398 | ||
5.3.4 Mechanism of thermal [?2+?2]?cycloadditions and [?2+?2]?cycloreversions: 1,4?diradical/zwitterion intermediates or diradicaloid transition structures | 400 | ||
5.3.5 Cycloadditions of allenes | 404 | ||
5.3.6 Cycloadditions of ketenes and keteniminium salts | 405 | ||
5.3.7 Wittig olefination | 412 | ||
5.3.8 Olefinations analogous to the Wittig reaction | 416 | ||
5.3.9 Diels–Alder reaction: concerted and non?concerted mechanisms compete | 419 | ||
5.3.10 Concerted Diels–Alder reactions with synchronous or asynchronous transition states | 423 | ||
5.3.11 Diradicaloid model for transition states of concerted Diels–Alder reactions | 424 | ||
5.3.12 Structural effects on the Diels–Alder reactivity | 429 | ||
5.3.13 Regioselectivity of Diels–Alder reactions | 431 | ||
5.3.14 Stereoselectivity of Diels–Alder reactions: the Alder “endo rule” | 438 | ||
5.3.15 ??Facial selectivity of Diels–Alder reactions | 440 | ||
5.3.16 Examples of hetero?Diels–Alder reactions | 443 | ||
5.3.17 1,3?Dipolar cycloadditions | 452 | ||
5.3.18 Sharpless asymmetric dihydroxylation of alkenes | 460 | ||
5.3.19 Thermal (2+2+2)?cycloadditions | 460 | ||
5.3.20 Noncatalyzed (4+3)? and (5+2)?cycloadditions | 463 | ||
5.3.21 Thermal higher order (m+n)?cycloadditions | 466 | ||
5.4 Cheletropic reactions | 469 | ||
5.4.1 Cyclopropanation by (2+1)?cheletropic reaction of carbenes | 469 | ||
5.4.2 Aziridination by (2+1)?cheletropic addition of nitrenes | 472 | ||
5.4.3 Decarbonylation of cyclic ketones by cheletropic elimination | 474 | ||
5.4.4 Cheletropic reactions of sulfur dioxide | 476 | ||
5.4.5 Cheletropic reactions of heavier congeners of carbenes and nitrenes | 479 | ||
5.5 Thermal sigmatropic rearrangements | 483 | ||
5.5.1 (1,2)?Sigmatropic rearrangement of carbenium ions | 483 | ||
5.5.2 (1,2)?Sigmatropic rearrangements of radicals | 488 | ||
5.5.3 (1,2)?Sigmatropic rearrangements of organoalkali compounds | 491 | ||
5.5.4 (1,3)?Sigmatropic rearrangements | 494 | ||
5.5.5 (1,4)?Sigmatropic rearrangements | 497 | ||
5.5.6 (1,5)?Sigmatropic rearrangements | 499 | ||
5.5.7 (1,7)?Sigmatropic rearrangements | 501 | ||
5.5.8 (2,3)?Sigmatropic rearrangements | 502 | ||
5.5.9 (3,3)?Sigmatropic rearrangements | 508 | ||
5.5.9.1 Fischer indole synthesis (3,4?diaza?Cope rearrangement) | 508 | ||
5.5.9.2 Claisen rearrangement and its variants (3?oxa?Cope rearrangements) | 508 | ||
5.5.9.3 Aza?Claisen rearrangements (3?aza?Cope rearrangements) | 513 | ||
5.5.9.4 Overman rearrangement (1?oxa?3?aza?Cope rearrangement) | 515 | ||
5.5.9.5 Thia?Claisen rearrangement (3?thia?Cope rearrangement) | 516 | ||
5.5.9.6 Cope rearrangements | 516 | ||
5.5.9.7 Facile anionic oxy?Cope rearrangements | 521 | ||
5.5.9.8 Acetylenic Cope rearrangements | 523 | ||
5.5.9.9 Other hetero?Cope rearrangements | 524 | ||
5.6 Dyotropic rearrangements and transfers | 527 | ||
5.6.1 Type I dyotropic rearrangements | 528 | ||
5.6.2 Alkene and alkyne reductions with diimide | 530 | ||
5.6.3 Type II dyotropic rearrangements | 531 | ||
5.7 Ene?reactions and related reactions | 532 | ||
5.7.1 Thermal Alder ene?reactions | 533 | ||
5.7.2 Carbonyl ene?reactions | 536 | ||
5.7.3 Other hetero?ene reactions involving hydrogen transfers | 536 | ||
5.7.4 Metallo?ene?reactions | 540 | ||
5.7.5 Carbonyl allylation with allylmetals: carbonyl metallo?ene?reactions | 541 | ||
5.7.6 Aldol reaction | 546 | ||
5.7.7 Reactions of metal enolates with carbonyl compounds | 550 | ||
References | 558 | ||
Chapter 6 Organic photochemistry | 647 | ||
6.1 Introduction | 647 | ||
6.2 Photophysical processes of organic compounds | 647 | ||
6.2.1 UV–visible spectroscopy: electronic transitions | 648 | ||
6.2.2 Fluorescence and phosphorescence: singlet and triplet excited states | 652 | ||
6.2.3 Bimolecular photophysical processes | 655 | ||
6.3 Unimolecular photochemical reactions of unsaturated hydrocarbons | 658 | ||
6.3.1 Photoinduced (E)/(Z)?isomerization of alkenes | 658 | ||
6.3.2 Photochemistry of cyclopropenes, allenes, and alkynes | 662 | ||
6.3.3 Electrocyclic ring closures of conjugated dienes and ring opening of cyclobutenes | 663 | ||
6.3.4 The di???methane (Zimmerman) rearrangement of 1,4?dienes | 665 | ||
6.3.5 Electrocyclic interconversions of cyclohexa?1,3?dienes and hexa?1,3,5?trienes | 667 | ||
6.4 Unimolecular photochemical reactions of carbonyl compounds | 669 | ||
6.4.1 Norrish type I reaction (??cleavage) | 669 | ||
6.4.2 Norrish type II reaction and other intramolecular hydrogen transfers | 671 | ||
6.4.3 Unimolecular photochemistry of enones and dienones | 674 | ||
6.5 Unimolecular photoreactions of benzene and heteroaromatic analogs | 676 | ||
6.5.1 Photoisomerization of benzene | 676 | ||
6.5.2 Photoisomerizations of pyridines, pyridinium salts, and diazines | 678 | ||
6.5.3 Photolysis of five?membered ring heteroaromatic compounds | 679 | ||
6.6 Photocleavage of carbon–heteroatom bonds | 681 | ||
6.6.1 Photo?Fries, photo?Claisen, and related rearrangements | 681 | ||
6.6.2 Photolysis of 1,2?diazenes, 3H?diazirines, and diazo compounds | 683 | ||
6.6.3 Photolysis of alkyl halides | 686 | ||
6.6.4 Solution photochemistry of aryl and alkenyl halides | 689 | ||
6.6.5 Photolysis of phenyliodonium salts: formation of aryl and alkenyl cation intermediates | 691 | ||
6.6.6 Photolytic decomposition of arenediazonium salts in solution | 692 | ||
6.7 Photocleavage of nitrogen?nitrogen bonds | 693 | ||
6.7.1 Photolysis of azides | 694 | ||
6.7.2 Photo?Curtius rearrangement | 696 | ||
6.7.3 Photolysis of geminal diazides | 697 | ||
6.7.4 Photolysis of 1,2,3?triazoles and of tetrazoles | 698 | ||
6.8 Photochemical cycloadditions of unsaturated compounds | 699 | ||
6.8.1 Photochemical intramolecular (2+2)?cycloadditions of alkenes | 700 | ||
6.8.2 Photochemical intermolecular (2+2)?cycloadditions of alkenes | 704 | ||
6.8.3 Photochemical intermolecular (4+2)?cycloadditions of dienes and alkenes | 708 | ||
6.8.4 Photochemical cycloadditions of benzene and derivatives to alkenes | 709 | ||
6.8.5 Photochemical cycloadditions of carbonyl compounds | 713 | ||
6.8.6 Photochemical cycloadditions of imines and related C?N double?bonded compounds | 718 | ||
6.9 Photo?oxygenation | 720 | ||
6.9.1 Reactions of ground?state molecular oxygen with hydrocarbons | 720 | ||
6.9.2 Singlet molecular oxygen | 723 | ||
6.9.3 Diels–Alder reactions of singlet oxygen | 727 | ||
6.9.4 Dioxa?ene reactions of singlet oxygen | 732 | ||
6.9.5 (2+2)?Cycloadditions of singlet oxygen | 736 | ||
6.9.6 1,3?Dipolar cycloadditions of singlet oxygen | 737 | ||
6.9.7 Nonpericyclic reactions of singlet oxygen | 739 | ||
6.10 Photoinduced electron transfers | 742 | ||
6.10.1 Marcus model | 743 | ||
6.10.2 Catalysis through photoreduction | 743 | ||
6.10.3 Photoinduced net reductions | 747 | ||
6.10.4 Catalysis through photo?oxidation | 749 | ||
6.10.5 Photoinduced net oxidations | 753 | ||
6.10.6 Generation of radical intermediates by PET | 756 | ||
6.10.7 Dye?sensitized solar cells | 758 | ||
6.11 Chemiluminescence and bioluminescence | 759 | ||
6.11.1 Thermal isomerization of Dewar benzene into benzene | 760 | ||
6.11.2 Oxygenation of electron?rich organic compounds | 761 | ||
6.11.3 Thermal fragmentation of 1,2?dioxetanes | 764 | ||
6.11.4 Peroxylate chemiluminescence | 766 | ||
6.11.5 Firefly bioluminescence | 766 | ||
References | 767 | ||
Chapter 7 Catalytic reactions | 827 | ||
7.1 Introduction | 827 | ||
7.2 Acyl group transfers | 830 | ||
7.2.1 Esterification and ester hydrolysis | 830 | ||
7.2.2 Acid or base?catalyzed acyl transfers | 831 | ||
7.2.3 Amphoteric compounds are good catalysts for acyl transfers | 834 | ||
7.2.4 Catalysis by nucleofugal group substitution | 834 | ||
7.2.5 N?heterocyclic carbene?catalyzed transesterifications | 836 | ||
7.2.6 Enzyme?catalyzed acyl transfers | 838 | ||
7.2.7 Mimics of carboxypeptidase A | 839 | ||
7.2.8 Direct amide bond formation from amines and carboxylic acids | 839 | ||
7.3 Catalysis of nucleophilic additions | 842 | ||
7.3.1 Catalysis of nucleophilic additions to aldehydes, ketones and imines | 842 | ||
7.3.2 Bifunctional catalysts for nucleophilic addition/elimination | 843 | ||
7.3.3 ?? and ??Nucleophiles as catalysts for nucleophilic additions to aldehydes and ketones | 844 | ||
7.3.4 Catalysis by self?assembled encapsulation | 845 | ||
7.3.5 Catalysis of 1,4?additions (conjugate additions) | 846 | ||
7.4 Anionic nucleophilic displacement reactions | 847 | ||
7.4.1 Pulling on the leaving group | 847 | ||
7.4.2 Phase transfer catalysis | 848 | ||
7.5 Catalytical Umpolung C?C bond forming reactions | 850 | ||
7.5.1 Benzoin condensation: Umpolung of aldehydes | 851 | ||
7.5.2 Stetter reaction: Umpolung of aldehydes | 853 | ||
7.5.3 Umpolung of enals | 854 | ||
7.5.4 Umpolung of Michael acceptors | 855 | ||
7.5.5 Rauhut–Currier reaction | 858 | ||
7.5.6 Morita–Baylis–Hillman reaction | 858 | ||
7.5.7 Nucleophilic catalysis of cycloadditions | 860 | ||
7.5.8 Catalysis through electron?transfer: hole?catalyzed reactions | 863 | ||
7.5.9 Umpolung of enamines | 866 | ||
7.5.10 Catalysis through electron?transfer: Umpolung through electron capture | 868 | ||
7.6 Brønsted and Lewis acids as catalysts in C?C bond forming reactions | 868 | ||
7.6.1 Mukaiyama aldol reactions | 871 | ||
7.6.2 Metallo?carbonyl?ene reactions | 875 | ||
7.6.3 Carbonyl?ene reactions | 878 | ||
7.6.4 Imine?ene reactions | 879 | ||
7.6.5 Alder?ene reaction | 880 | ||
7.6.6 Diels–Alder reaction | 881 | ||
7.6.7 Brønsted and Lewis acid?catalyzed hetero?Diels?Alder reactions | 883 | ||
7.6.8 Acid?catalyzed (2+2)?cycloadditions | 885 | ||
7.6.9 Lewis acid catalyzed (3+2)? and (3+3)?cycloadditions | 887 | ||
7.6.10 Lewis acid promoted (5+2)?cycloadditions | 889 | ||
7.7 Bonding in transition metal complexes and their reactions | 890 | ||
7.7.1 The ??complex theory | 890 | ||
7.7.2 The isolobal formalism | 892 | ||
7.7.3 ??Complexes of dihydrogen | 895 | ||
7.7.4 ??Complexes of C?H bonds and agostic bonding | 898 | ||
7.7.5 ??Complexes of C?C bonds and C?C bond activation | 899 | ||
7.7.6 Reactions of transition metal complexes are modeled by reactions of organic chemistry | 901 | ||
7.7.7 Ligand exchange reactions | 901 | ||
7.7.8 Oxidative additions and reductive eliminations | 905 | ||
7.7.9 ??Insertions/??eliminations | 912 | ||
7.7.10 ??Insertions/??eliminations | 915 | ||
7.7.11 ??Cycloinsertions/??cycloeliminations: metallacyclobutanes, metallacyclobutenes | 918 | ||
7.7.12 Metallacyclobutenes: alkyne polymerization, enyne metathesis, cyclopentadiene synthesis | 919 | ||
7.7.13 Metallacyclobutadiene: alkyne metathesis | 921 | ||
7.7.14 Matallacyclopentanes, metallacyclopentenes, metallacyclopentadienes: oxidative cyclizations (??cycloinsertions) and reductive fragmentations (??cycloeliminations) | 922 | ||
7.8 Catalytic hydrogenation | 923 | ||
7.8.1 Heterogeneous catalysts for alkene, alkyne, and arene hydrogenation | 924 | ||
7.8.2 Homogeneous catalysts for alkene and alkyne hydrogenation | 926 | ||
7.8.3 Dehydrogenation of alkanes | 929 | ||
7.8.4 Hydrogenation of alkynes into alkenes | 929 | ||
7.8.5 Catalytic hydrogenation of arenes and heteroarenes | 931 | ||
7.8.6 Catalytic hydrogenation of ketones and aldehydes | 931 | ||
7.8.7 Catalytic hydrogenation of carboxylic acids, their esters and amides | 934 | ||
7.8.8 Hydrogenation of carbon dioxide | 935 | ||
7.8.9 Catalytic hydrogenation of nitriles and imines | 936 | ||
7.8.10 Catalytic hydrogenolysis of C–halogen and C–chalcogen bonds | 938 | ||
7.9 Catalytic reactions of silanes | 938 | ||
7.9.1 Reduction of alkyl halides | 938 | ||
7.9.2 Reduction of carbonyl compounds | 939 | ||
7.9.3 Alkene hydrosilylation | 941 | ||
7.10 Hydrogenolysis of C?C single bonds | 942 | ||
7.11 Catalytic oxidations with molecular oxygen | 943 | ||
7.11.1 Heme?dependent monooxygenase oxidations | 944 | ||
7.11.2 Chemical aerobic C?H oxidations | 946 | ||
7.11.3 Reductive activation of molecular oxygen | 949 | ||
7.11.4 Oxidation of alcohols with molecular oxygen | 950 | ||
7.11.5 Wacker process | 952 | ||
7.12 Catalyzed nucleophilic aromatic substitutions | 954 | ||
7.12.1 Ullmann–Goldberg reactions | 955 | ||
7.12.2 Buchwald–Hartwig reactions | 958 | ||
References | 959 | ||
Chapter 8 Transition?metal?catalyzed C?C bond forming reactions | 1061 | ||
8.1 Introduction | 1061 | ||
8.2 Organic compounds from carbon monoxide | 1062 | ||
8.2.1 Fischer–Tropsch reactions | 1062 | ||
8.2.2 Carbonylation of methanol | 1064 | ||
8.2.3 Hydroformylation of alkenes | 1066 | ||
8.2.4 Silylformylation | 1071 | ||
8.2.5 Reppe carbonylations | 1073 | ||
8.2.6 Pd(II)?mediated oxidative carbonylations | 1074 | ||
8.2.7 Pauson–Khand reaction | 1075 | ||
8.2.8 Carbonylation of halides: synthesis of carboxylic derivatives | 1079 | ||
8.2.9 Reductive carbonylation of halides: synthesis of carbaldehydes | 1081 | ||
8.2.10 Carbonylation of epoxides and aziridines | 1082 | ||
8.2.11 Hydroformylation and silylformylation of epoxides | 1085 | ||
8.3 Direct hydrocarbation of unsaturated compounds | 1085 | ||
8.3.1 Hydroalkylation of alkenes: alkylation of alkanes | 1086 | ||
8.3.2 Alder ene?reaction of unactivated alkenes and alkynes | 1088 | ||
8.3.3 Hydroarylation of alkenes: alkylation of arenes and heteroarenes | 1089 | ||
8.3.4 Hydroarylation of alkynes: alkenylation of arenes and heteroarenes | 1092 | ||
8.3.5 Hydroarylation of carbon?heteroatom multiple bonds | 1094 | ||
8.3.6 Hydroalkenylation of alkynes, alkenes, and carbonyl compounds | 1094 | ||
8.3.7 Hydroacylation of alkenes and alkynes | 1095 | ||
8.3.8 Hydrocyanation of alkenes and alkynes | 1098 | ||
8.3.9 Direct reductive hydrocarbation of unsaturated compounds | 1099 | ||
8.3.10 Direct hydrocarbation via transfer hydrogenation | 1101 | ||
8.4 Carbacarbation of unsaturated compounds and cycloadditions | 1102 | ||
8.4.1 Formal [?2+?2]?cycloadditions | 1104 | ||
8.4.2 (2+1)?Cycloadditions | 1104 | ||
8.4.3 Ohloff–Rautenstrauch cyclopropanation | 1109 | ||
8.4.4 [?2+?2]?Cycloadditions | 1110 | ||
8.4.5 (3+1)?Cycloadditions | 1112 | ||
8.4.6 (3+2)?Cycloadditions | 1113 | ||
8.4.7 (4+1)?Cycloadditions | 1119 | ||
8.4.8 (2+2+1)?Cycloadditions | 1121 | ||
8.4.9 [?4+?2]?Cycloadditions of unactivated cycloaddents | 1122 | ||
8.4.10 (2+2+2)?Cycloadditions | 1128 | ||
8.4.11 (3+3)?Cycloadditions | 1133 | ||
8.4.12 (3+2+1)?Cycloadditions | 1134 | ||
8.4.13 (4+3)?Cycloadditions | 1135 | ||
8.4.14 (5+2)?Cycloadditions | 1137 | ||
8.4.15 (4+4)?Cycloadditions | 1140 | ||
8.4.16 (4+2+2)?Cycloadditions | 1141 | ||
8.4.17 (6+2)?Cycloadditions | 1142 | ||
8.4.18 (2+2+2+2)?Cycloadditions | 1143 | ||
8.4.19 (5+2+1)?Cycloadditions | 1144 | ||
8.4.20 (7+1)?Cycloadditions | 1144 | ||
8.4.21 Further examples of high?order catalyzed cycloadditions | 1144 | ||
8.4.22 Annulations through catalytic intramolecular hydrometallation | 1147 | ||
8.4.23 Oxidative annulations | 1147 | ||
8.5 Didehydrogenative C?C?coupling reactions | 1148 | ||
8.5.1 Glaser–Hay reaction: oxidative alkyne homocoupling | 1148 | ||
8.5.2 Oxidative C?C cross?coupling reactions | 1149 | ||
8.5.3 Oxidative aryl/aryl homocoupling reactions | 1151 | ||
8.5.4 Oxidative aryl/aryl cross?coupling reactions | 1153 | ||
8.5.5 TEMPO?cocatalyzed oxidative C?C coupling reactions | 1154 | ||
8.5.6 Oxidative aminoalkylation of alkynes and active C?H moieties | 1155 | ||
8.6 Alkane, alkene, and alkyne metathesis | 1156 | ||
8.6.1 Alkane metathesis | 1157 | ||
8.6.2 Alkene metathesis | 1158 | ||
8.6.3 Enyne metathesis: alkene/alkyne cross?metathesis | 1163 | ||
8.6.4 Alkyne metathesis | 1165 | ||
8.7 Additions of organometallic reagents | 1166 | ||
8.7.1 Additions of Grignard reagents | 1168 | ||
8.7.2 Additions of alkylzinc reagents | 1174 | ||
8.7.3 Additions of organoaluminum compounds | 1175 | ||
8.7.4 Additions of organoboron, silicium , and zirconium compounds | 1177 | ||
8.8 Displacement reactions | 1180 | ||
8.8.1 Kharash cross?coupling and Kumada–Tamao–Corriu reaction | 1180 | ||
8.8.2 Negishi cross?coupling | 1186 | ||
8.8.3 Stille cross?coupling and carbonylative Stille reaction | 1189 | ||
8.8.4 Suzuki–Miyaura cross?coupling | 1193 | ||
8.8.5 Hiyama cross?coupling | 1198 | ||
8.8.6 Tsuji–Trost reaction: allylic alkylation | 1200 | ||
8.8.7 Mizoroki–Heck coupling | 1203 | ||
8.8.8 Sonogashira–Hagihara cross?coupling | 1211 | ||
8.8.9 Arylation of arenes(heteroarenes) with aryl(heteroaryl) derivatives | 1214 | ||
8.8.10 ??Arylation of carbonyl compounds and nitriles | 1219 | ||
8.8.11 Direct arylation and alkynylation of nonactivated C?H bonds in alkyl groups | 1221 | ||
8.8.12 Direct alkylation of nonactivated C?H bonds in alkyl groups | 1222 | ||
References | 1223 | ||
Index | 1349 | ||
EULA | 1385 |