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Organic Synthesis Using Transition Metals, 2nd Edition



Organic Synthesis Using Transition Metals, 2nd Edition

Roderick Bates

ISBN: 978-1-118-31366-4 April 2012 464 Pages

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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.

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 η-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 η3- or π-Allyl Complexes 325

9.1 Stoichiometric Reactions of π-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 η4-Diene Complexes 361

10.2 η5-Dienyl Complexes 371

10.3 η6-Arene Complexes 377

10.4 η2-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

  • new chapter on C-H activation
  • includes a survey of the range of ligands developed for transition metal chemistry, from phosphines to NHCs
  • discussion of the key features of organic catalysis: how to draw a catalytic cycle; and how catalysis contributes to atom economy and green chemistry
  • coverage of Hiyama coupling, including the recent modifications of this reaction by Denmark and others. 
  • the heteroatom coupling and enolate coupling sections are greatly expanded, mainly due to the extensive work of Hatwig and Buchwald. 
  • new developments in sp3-sp3 coupling reactons are highlighted
  • coupling without using palladium, including the Nozaki-Kishi reaction, are described
  • expanded coverage of hydroformylation, particularly with the recent development of directed hydroformylation
  • discussion of the Kulinkovich reaction
  • includes much more material on gold chemistry
  • the section on alkene metathesis is greatly expanded, including cross-metathesis and relay metathesis
  • sections on asymmetric reactions are added to various chapters, including alkene and insertions (asymmetric Heck, Hoveyda chemistry), metathesis, ƒà-allyl complexes. 
  • Larger portions of total syntheses are highlighted, to put the transition metal chemistry into greater context.
  • Special topics, such as tandem reactions, reactions that combine transition metals with other methods, solid supported reactions and flow reactions are demonstrated by examples at appropriate points.
  • Includes key references and an index of compounds

“In conclusion, this is an outstanding book which should be of value to all process chemists, as well as to postgraduate students.”  (Organic Process Research & Development Journal, 1 April 2013)

“This fine work, which includes an excellent bibliography, in the field of catalysis will be useful for professional chemists; it also will be a valuable resource for graduate students.  Highly recommended.  Graduate students, researchers/faculty, and professionals/practitioners.”  (Choice,  1 December 2012)