Organic synthesis using transition metals / Roderick Bates.

Format:

Book

Author/Creator:

Bates, Roderick, author.

Contributor:

ProQuest (Firm)

Language:

English

Subjects (All):

Organic compounds--Synthesis.

Organic compounds.

Transition metals.

Genre:

Electronic books.

Physical Description:

1 online resource (xi, 446 pages) : illustrations

Edition:

Second edition.

Place of Publication:

Chichester, West Sussex : Wiley, 2012.

System Details:

text file

Summary:

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.

Organic Synthesis Using transition Metals, Second Edition considers the ways in which transition metals, as catalysts and reagents, can be used in organic synthesis. It concentrates on the bond-forming reactions that set transition metal chemistry apart from "classical" organic chemistry.

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. Each chapter is extensively referenced and provides a convenient point of entry to the research literature.

Organic Synthesis Using Transition Metals, Second 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 be useful for practising researchers who want to refresh and enhance their knowledge of the field. Book jacket.

Contents:

1 Introduction 1

1.1 The Basics 2

1.2 The Basic Structural Types 2

1.2.1 Phosphines 5

1.2.2 Phosphites 8

1.2.3 N-Heterocyclic Carbenes 9

1.2.4 Other Ligands 10

1.2.5 Quantifying Ligand Effects 10

1.2.6 Heterogeneous Catalysis 10

1.3 Just How Many Ligands Can Fit around a Metal Atom? 10

1.3.1 Method 1: Covalent 11

1.3.2 Method 2: Ionic 11

1.3.3 Examples 12

1.4 Mechanism and the Basic Reaction Steps 13

1.4.1 Coordination and Dissociation 13

1.4.2 Oxidative Addition and Reductive Elimination 15

1.4.3 Transmetallation 15

1.4.4 Alkene and Alkyne Insertion 15

1.4.5 CO Insertion 16

1.4.6 β-Hydride Elimination 16

1.4.7 Oxidative Cyclization 17

1.5 Catalysis 17

References 19

2 Coupling Reactions 21

2.1 Carbon-Carbon Bond Formation 21

2.1.1 The Main-Group Metal, M 22

2.1.2 Limitation 23

2.1.3 Reactivity of the Leaving Group 23

2.1.4 Selectivity 25

2.1.4.1 Selectivity Based on Halogen Reactivity 25

2.1.4.2 Steric Hindrance 25

2.1.4.3 Electronic Effects 26

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

2.5.1 Vinyl Stannanes 41

2.5.2 Aryl and Heteroaryl Stannanes 42

2.5.3 The Intramolecular Stille Reaction 42

2.5.4 Coupling of Acid Chlorides 42

2.5.5 Stille Coupling of Triflates 44

2.5.6 Stille Coupling of Alkyl Halides 44

2.5.7 Stille Reaction Troubleshooting 44

2.6 Boron: The Suzuki Reaction 46

2.6.1 Alkenyl Borane Coupling Reactions 48

2.6.2 Alkyl Borane Coupling Reactions 50

2.6.3 Aryl Borane Coupling Reactions 52

2.6.4 Suzuki Coupling of AlkylHalides 56

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

2.12.1 Palladium-Catalysed Synthesis of Amine Derivatives 72

2.12.2 Palladium-Catalysed Synthesis of Ethers 76

2.12.3 Ullmann Coupling 78

2.12.4 Formation of Other C-X bonds 81

References 82

3 C-H Activation 89

3.1 Arenes and Heteroarenes 91

3.1.1 Fujiwara-Heck Reaction 91

3.1.2 Biaryl Coupling 93

3.2 Aldehydes 100

3.3 Borylation and Silylation 102

3.4 Allylic Functionalization 103

3.5 Unfunctionalized C-H Bonds 105

3.5.1 Carbon-Heteroatom Bond Formation 105

3.5.2 Carbon-Carbon Bond Formation 109

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

4.3.1 The Carbonylative Heck Reaction 127

4.3.2 Other Carbonylation Reactions of Allenes and Alkynes 129

4.4 Hydroformylation 130

4.4.1 Directed Hydroformylation 135

4.4.2 Asymmetric Hydroformylation 138

4.5 Stoichiometric Carbonylation Using Carbonyl Complexes 139

4.5.1 Iron and Cobalt Carbonyl Anions 139

4.5.2 Ferrilactones and Ferrilactams 142

4.5.3 Molybdenum and Tungsten Carbonyls 145

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

5.1.1 The Organic Halide 153

5.1.2 Leaving Groups 155

5.1.3 Catalysts, Ligands and Reagents 158

5.1.4 The Alkene: Scope and Reactivity 159

5.1.5 The Alkene: Regio- and Stereoselectivity 160

5.1.6 Cyclic Alkenes 161

5.1.7 Isomerization 162

5.1.8 The Intramolecular Heck Reaction 163

5.1.9 The Asymmetric Heck Reaction 164

5.1.10 Tandem Reactions 169

5.1.10.1 Alkynes 169

5.1.10.2 Trisubstituted Alkenes 171

5.1.10.3 Rigid Alkenes 172

5.1.11 Heck-Like Reactions of Organometallics 174

5.2 Insertion Reactions Involving Zirconium and Titanium 175

5.2.1 Hydrozirconation and Carbozirconation 175

5.2.2 Alkene and Alkyne Complexes 177

5.2.3 Zirconium-Mediated Carbomagnesiation 182

5.2.4 The Kulinkovich Reaction 185

References 188

6 Electrophilic Alkene and Alkyne Complexes 191

6.1 Electrophilic Palladium Complexes 191

6.1.1 Tandem Reactions Involving CO or Alkene Insertion 198

6.1.2 Tandem Reactions with Oxidative Addition 207

6.2tOther Metals: Silver, Gold, Platinum and Rare Earths 210

6.2.1 Reactions of Alkenes 210

6.2.2 Reactions of Allenes 213

6.2.3 Reactions of Alkynes 216

6.2.4 The Hashmi Phenol Synthesis 223

6.2.5 Ene-Yne Cyclization 225

6.3 Iron 229

6.3.1 Fp Complexes of Alkenes 229

6.3.2 Fp Complexes of Alkynes 234

6.3.3 Alkylation of Allyl Fp Complexes and Formal Cycloadditions 234

6.4 Cobaloxime π-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

7.3.1 Asymmetric Pauson-Khand Reaction 248

7.3.2 The Hetero-Pauson-Khand Reaction 249

7.4 Synthesis Using Multiple Cobalt Reactions 250

References 251

8 Carbene Complexes 253

8.1 Fischer Carbenes 253

8.1.1 Demetallation 258

8.1.2 The Dötz Reaction 258

8.1.3 Not the Dötz Reaction 263

8.1.4 Fischer Carbene Photochemistry 267

8.2 Vinylidene Complexes 269

8.3 Metathesis Reactions Involving Carbene Complexes 273

8.3.1 Tebbe's Reagent 274

8.3.2 Alkene (Olefin) Metathesis 278

8.3.3 Ring-Closing Metathesis 279

8.3.4 Cross-Metathesis 291

8.3.5 Ring-Opening Metathesis 296

8.3.6 Asymmetric Metathesis 297

8.3.7 Ene-Yne Metathesis 300

8.3.8 Ene-Yne-Ene Metathesis 303

8.3.9 Tandem Reactions 306

8.3.10 Metathesis Side Reactions 306

8.4 Carbyne Complexes 310

8.4.1 Alkyne Metathesis 310

8.5 Carbene Complexes from Diazo Compounds 312

8.5.1 Nucleophilic Trapping 313

8.5.2 C-H Insertion Reactions of Carbene Complexes 315

8.5.3 C-H Insertion Reactions of Nitrene Complexes 316

References 319

9 η³- or π-Allyl Complexes 325

9.1 Stoichiometric Reactions of π-Allyl Complexes 325

9.2 Catalysis: Mostly Palladium 328

9.2.1 Regioselectivity 331

9.2.2 Internal versus Terminal Attack 333

9.2.3 Stereoselectivity 335

9.2.4 Asymmetric Allylation 337

9.2.5 Synthesis Using Palladium Allyl Chemistry 341

9.2.6 Base-Free Allylation 343

9.2.7 Allylation with Decarboxylation 347

9.2.8 Allyl as a Protecting Group 350

9.2.9 Other Routes to η³- or π-Allyl Palladium Complexes 352

9.3 Propargyl Compounds 357

References 357

10 Diene, Dienyl and Arene Complexes 361

10.1 η⁴-Diene Complexes 361

10.1.1 Electrophilic Attack 364

10.1.2 Nucleophilic Attack 366

10.1.3 Deprotonation 370

10.2 η⁵ -Dienyl Complexes 371

10.2.1 Nucleophilic Attack 372

10.3 η⁶-Arene Complexes 377

10.3.1 Nucleophilic Attack 380

10.3.2 Deprotonation 385

10.4 η²-Arene Complexes 387

References 389

11 Cycloaddition and Cycloisomerization Reactions 391

11.1 Formal Six-Electron, Six-Atom Cycloadditions 391

11.1.1 The [4 + 2] Cycloaddition 391

11.1.2 The [2 + 2 + 2] Cycloaddition 394

11.2 Cycloadditions Involving Fewer than Six Atoms 402

11.2.1 Four-Membered Rings 402

11.2.2 Five-Membered Rings through TMM Methods 402

11.2.3 Other Five-Membered Ring Formations 405

11.3 Cycloadditions Involving More than Six Atoms 407

11.3.1 The [5 + 2] Cycloaddition 407

11.3.2 The [4 + 4] Cycloaddition 410

11.3.3 The [6 + 2] and [6 + 4] Cycloadditions 411

11.4 Isomerization 414

11.5 Cycloisomerization and Related Reactions 415

References 426.

Notes:

Includes bibliographical references and index.

Electronic reproduction. Ann Arbor, MI : ProQuest, 2015. Available via World Wide Web. Access may be limited to ProQuest affiliated libraries.

OCLC:

775591927

Access Restriction:

Restricted for use by site license.