Organic Synthesis Using Transition Metals de Roderick Bates

Organic Synthesis Using Transition Metals

Roderick Bates

en Limba Engleză Paperback – 13 apr 2012

Transition metals open up new opportunities for synthesis, because their means of bonding and their reaction mechanisms differ from those of the elements of the s and p blocks. In the last two decades the subject has mushroomed - established reactions are seeing both technical improvements and increasing numbers of applications, and new reactions are being developed. The practicality of the subject is demonstrated by the large number of publications coming from the process development laboratories of pharmaceutical companies, and its importance is underlined by the fact that three Nobel prizes have been awarded for discoveries in this field in the 21st Century already.

Organic Synthesis Using Transition Metals, 2nd Edition considers the ways in which transition metals, as catalysts and reagents, can be used in organic synthesis, both for pharmaceutical compounds and for natural products. It concentrates on the bond-forming reactions that set transition metal chemistry apart from "classical" organic chemistry. Each chapter is extensively referenced and provides a convenient point of entry to the research literature. Topics covered include:

introduction to transition metals in organic synthesis
coupling reactions
C-H activation
carbonylative coupling reactions
alkene and alkyne insertion reactions
electrophilic alkene and alkyne complexes
reactions of alkyne complexes
carbene complexes
h³- or p-allyl -allyl complexes
diene, dienyl and arene complexes
cycloaddition and cycloisomerisation reactions

For this second edition the text has been extensively revised and expanded to reflect the significant improvements and advances in the field since the first edition, as well as the large number of new transition metal-catalysed processes that have come to prominence in the last 10 years - for example the extraordinary progress in coupling reactions using "designer" ligands, catalysis using gold complexes, new opportunities arising from metathesis chemistry, and C-H activation - without neglecting the well established chemistry of metals such as palladium.
Organic Synthesis Using Transition Metals, 2nd Edition will find a place on the bookshelves of advanced undergraduates and postgraduates working in organic synthesis, catalysis, medicinal chemistry and drug discovery. It is also useful for practising researchers who want to refresh and enhance their knowledge of the field.

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About the Author xiii Preface xv 1 Introduction 1 1.1 The Basics 2 1.2 The Basic Structural Types 2 1.3 Just How Many Ligands Can Fit around a Metal Atom? 10 1.4 Mechanism and the Basic Reaction Steps 13 1.5 Catalysis 17 References 19 2 Coupling Reactions 21 2.1 Carbon-Carbon Bond Formation 21 2.2 Lithium and Magnesium: Kumada Coupling 27 2.3 Zinc: The Negishi Reaction 32 2.4 Aluminium and Zirconium 35 2.5 Tin: The Stille Reaction 37 2.6 Boron: The Suzuki Reaction 46 2.7 Silicon: The Hiyama Reaction 57 2.8 Copper: The Sonogashira Reaction 61 2.9 Other Metals 67 2.10 Homocoupling 67 2.11 Enolate and Phenoxide Coupling 69 2.12 Heteroatom Coupling 70 References 82 3 C-H Activation 89 3.1 Arenes and Heteroarenes 91 3.2 Aldehydes 100 3.3 Borylation and Silylation 102 3.4 Allylic Functionalization 103 3.5 Unfunctionalized C-H Bonds 105 References 115 4 Carbonylation 117 4.1 Carbonylative Coupling Reactions: Synthesis of Carbonyl Derivatives 117 4.2 Carbonylative Coupling Reactions: Synthesis of Carboxylic Acid Derivatives 122 4.3 Carbonylation of Alkenes and Alkynes 127 4.4 Hydroformylation 130 4.5 Stoichiometric Carbonylation Using Carbonyl Complexes 139 4.6 Carboxylation 146 4.7 Decarbonylation and Decarboxylation 148 References 150 5 Alkene and Alkyne Insertion Reactions 153 5.1 The Heck Reaction 153 5.2 Insertion Reactions Involving Zirconium and Titanium 175 References 188 6 Electrophilic Alkene and Alkyne Complexes 191 6.1 Electrophilic Palladium Complexes 191 6.2 Other Metals: Silver, Gold, Platinum and Rare Earths 210 6.3 Iron 229 6.4 Cobaloxime _-Cations 235 References 237 7 Reactions of Alkyne Complexes 241 7.1 Alkyne Cobalt Complexes 241 7.2 Propargyl Cations: The Nicholas Reaction 244 7.3 The Pauson-Khand Reaction 246 7.4 Synthesis Using Multiple Cobalt Reactions 250 References 251 8 Carbene Complexes 253 8.1 Fischer Carbenes 253 8.2 Vinylidene Complexes 269 8.3 Metathesis Reactions Involving Carbene Complexes 273 8.4 Carbyne Complexes 310 8.5 Carbene Complexes from Diazo Compounds 312 References 319 9 eta3- or pi-Allyl Complexes 325 9.1 Stoichiometric Reactions of pi-Allyl Complexes 325 9.2 Catalysis: Mostly Palladium 328 9.3 Propargyl Compounds 357 References 357 10 Diene, Dienyl and Arene Complexes 361 10.1 eta4-Diene Complexes 361 10.2 eta5-Dienyl Complexes 371 10.3 eta6-Arene Complexes 377 10.4 eta2-Arene Complexes 387 References 389 11 Cycloaddition and Cycloisomerization Reactions 391 11.1 Formal Six-Electron, Six-Atom Cycloadditions 391 11.2 Cycloadditions Involving Fewer than Six Atoms 402 11.3 Cycloadditions Involving More than Six Atoms 407 11.4 Isomerization 414 11.5 Cycloisomerization and Related Reactions 415 References 426 Abbreviations 431 Index of Principle Transition Metal Catalysts and Reagents 433 Index 437