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Palladium-Catalyzed Coupling Reactions. Practical Aspects and Future Developments

  • ID: 2329798
  • April 2013
  • 692 Pages
  • John Wiley and Sons Ltd

This handbook and ready reference brings together all significant issues of practical importance in selected topics discussing recent
significant achievements for interested readers in one single volume. While covering homogeneous and heterogeneous catalysis, the text is unique in focusing on such important aspects as using different reaction media, microwave techniques or catalyst recycling. It also provides a comprehensive treatment of key issues of modern-day coupling reactions having emerged and matured in recent years and emphasizes those topics that show potential for future development, such as continuous flow systems, water as a reaction medium, and catalyst immobilization, among others.

With its inclusion of large-scale applications in the pharmaceutical industry, this will equally be of great interest to industrial chemists.

From the contents
- Palladium-Catalyzed Cross-Coupling Reactions - A General Introduction
- High-turnover Heterogeneous Palladium Catalysts in Coupling Reactions: the Case of Pd Loaded on Dealuminated Y Zeolites
Palladium-Catalyzed Coupling Reactions with Magnetically Separable Nanocatalysts
- The Use of Ordered Porous Solids READ MORE >

Note: Product cover images may vary from those shown

Foreword XIII

Preface XV

List of Contributors XVII

1 Palladium-Catalyzed Cross-Coupling Reactions – A General Introduction 1
Klaus Kohler, Katharina Wussow, and Andreas Sebastian Wirth

1.1 Introduction 1

1.1.1 Historical Reflection 1

1.1.2 Characteristics, Recent Developments, and Progress 2

1.1.3 Literature Reviews and Organization of the Chapter 3

1.2 Carbon–Carbon Cross-Coupling Reactions Catalyzed by Palladium 4

1.2.1 Classification and Overview 4

1.2.2 Common Mechanistic Features of Cross-Coupling Reactions and Reactivity of the Substrates 8

1.2.2.1 Choice of the Carbon Electrophile 9

1.2.2.2 Choice of the Carbon Nucleophile – What Makes the Difference? 9

1.3 The Catalysts 10

1.3.1 The Particular Features of Palladium 10

1.3.2 Classes of Palladium Catalysts Applied to Cross-Coupling Reactions 12

1.3.2.1 Ligands and Palladium Complexes – Homogeneous Systems 13

1.3.2.2 Immobilized or Supported Palladium Complexes and Particles – Heterogeneous Systems 17

1.3.2.3 Palladium Colloids and (Nonsupported) Nanoparticles 17

1.3.2.4 Activity of Heterogeneous Catalysts 18

1.4 Mechanistic Aspects 18

1.4.1 General Mechanism of CC Cross-Coupling and Heck Reactions with Homogeneous Catalyst Precursors 18

1.4.2 Models for Heck and Suzuki Reactions with Supported Pd Precursors 19

1.4.3 Recent Results on the Reaction Mechanism and the Nature of the Active Pd Species 21

1.4.3.1 Observation of Intermediates in Homogeneous Catalysis by Electrochemical Methods 21

1.4.3.2 The Question of Pd Leaching 22

1.4.3.3 Selectivity Pattern 23

1.4.3.4 In Situ Observation by Spectroscopic Methods 24

1.4.3.5 Immobilized Pd Pincer Complexes 24

1.4.3.6 Palladium Bulk Materials (Pd Foil, Wire, Sponge) as Catalyst 24

1.5 Future Challenges 25

Abbreviations 27

References 27

2 High-Turnover Heterogeneous Palladium Catalysts in Coupling Reactions: the Case of Pd Loaded on Dealuminated Y Zeolites 31
Kazu Okumura

2.1 Introduction 31

2.2 Various Methodologies to Afford High Turnover Numbers Over Supported Pd Catalysts 32

2.3 Structure and Characteristics of Ultrastable Y Zeolites 33

2.4 Suzuki–Miyaura Reactions Catalyzed by Pd/USY 35

2.4.1 Catalytic Performance of Pd/USY 35

2.4.2 Pd Leaching from Pd/USY 40

2.4.3 Selectivity in the Homocoupling Reactions 41

2.4.4 Characterization of the Active Pd Species by X-Ray Absorption Spectroscopy 41

2.4.5 A Suggested Mechanism for the Formation of Active Pd Species in Suzuki–Miyaura Coupling Reactions 46

2.5 Catalytic Performance of Pd/USY in Mizoroki–Heck Reactions 48

2.5.1 Effect of H2 Bubbling on the Catalytic Reactions of Pd/USY 48

2.5.2 Catalytic Reactions Using Chlorobenzene Derivatives 51

2.5.3 Characterization of the Pd Species by X-Ray Absorption Spectroscopy 53

2.6 Conclusion and Perspective 54

Abbreviations 55

References 55

3 Palladium-Catalyzed Coupling Reactions with Magnetically Separable Nanocatalysts 57
Kifah S.M. Salih and Werner R. Thiel

3.1 Introduction 57

3.2 General Considerations Concerning Magnetic Particles as Catalyst Supports 57

3.3 Palladium Nanoparticles on Magnetic Supports 59

3.4 Molecular Palladium Complexes on Magnetic Supports 68

3.5 Outlook 75

Abbreviations 76

References 77

4 The Use of Ordered Porous Solids as Support Materials in Palladium-Catalyzed Cross-Coupling Reactions 79
Arpad Molnar

4.1 Introduction 79

4.2 Catalyst Synthesis and Characterization 80

4.3 Carbon–Carbon Couplings 85

4.3.1 Zeolites 85

4.3.2 Mesoporous Ordered Silica Materials 94

4.3.2.1 Coupling Reactions Catalyzed by Supported Palladium Particles 94

4.3.2.2 Reactions Mediated by Immobilized Palladium Species 103

4.3.3 Periodic Mesoporous Organosilicas 116

4.3.4 Catalysts Based on Nonsiliceous Solids 121

4.3.4.1 Metal–Organic Frameworks 121

4.3.4.2 Covalent Organic Frameworks 123

4.3.4.3 Other Support Materials 124

4.4 Miscellaneous Coupling Reactions 127

4.5 The Question of Solution-Phase Catalysis 130

4.6 Summary and Future Prospects 131

Abbreviations 133

References 134

5 Coupling Reactions Induced by Polymer-Supported Catalysts 141
Babak Karimi, Sedigheh Abedi, and Asghar Zamani

5.1 Introduction 141

5.2 Polysaccharides 143

5.2.1 Starch 143

5.2.2 Chitosan 145

5.2.3 Other Polysaccharides 148

5.3 Poly(ethylene glycol) 150

5.3.1 Nonfunctionalized Poly(ethylene glycol) 150

5.3.2 Functionalized Poly(ethylene glycol) 152

5.4 Polystyrene 155

5.4.1 Nonfunctionalized Polystyrene 155

5.4.2 Functionalized Polystyrene 156

5.4.2.1 Polystyrene-Supported Ligands Containing Nitrogen 156

5.4.2.2 Polystyrene-Supported Triphenylphosphane 161

5.5 Poly(norbornene) 165

5.6 Polyacrylamide 167

5.7 Polyaniline 170

5.8 Poly(N-vinyl-2-pyrrolidone) 171

5.9 Polypyrrole 173

5.10 Poly(4-vinylpyridine) 174

5.11 Ionic Polymers 175

5.11.1 Organic Polymers Containing N-Heterocyclic Carbenes or Ionic Liquids 176

5.11.2 Polymers Containing Other Ionic Ligands 183

5.12 Organometallic Polymers 184

5.13 Functionalized Porous Organic Polymers 188

5.14 Miscellaneous Polymers 189

5.15 Summary and Outlook 192

Abbreviations 193

References 195

6 Coupling Reactions in Ionic Liquids 201
Michael T. Keßler, Jackson D. Scholten, Frank Galbrecht, and Martin H.G. Prechtl

6.1 Introduction 201

6.2 Metal Complexes 204

6.2.1 Mizoroki–Heck Reaction 205

6.2.2 Sonogashira Coupling 209

6.2.3 Suzuki–Miyaura Coupling 212

6.2.4 Negishi Coupling 213

6.2.5 Trost–Tsuji Coupling 214

6.3 Metal Salts and Metal on Solid Support 214

6.3.1 Mizoroki–Heck Reaction 215

6.3.2 Suzuki–Miyaura Reaction 218

6.3.3 Stille Reaction 219

6.4 Metal Nanoparticles 220

6.4.1 The Mizoroki–Heck Reaction with PdNPs in ILs 222

6.4.2 Suzuki–Miyaura Reaction 224

6.4.3 Stille Reaction 226

6.4.4 Buchwald–Hartwig Reaction 227

6.4.5 Sonogashira Reaction 228

6.4.6 Ullmann Reaction 228

6.5 Summary and Outlook 229

Abbreviations 230

References 231

7 Cross-Coupling Reactions in Aqueous Media 235
Kevin H. Shaughnessy

7.1 Introduction 235

7.2 Cross-Coupling of Organic Halides to Form CC Bonds in Aqueous Media 236

7.2.1 Suzuki Coupling 236

7.2.1.1 Aqueous-Phase Suzuki Coupling Using Hydrophilic Ligand-Supported Catalysts 237

7.2.1.2 On Water Suzuki Couplings with Hydrophobic Catalyst Systems 248

7.2.1.3 Surfactant-Promoted Aqueous-Phase Suzuki Couplings 249

7.2.1.4 Palladium Catalysts Supported on Heterogeneous Supports 251

7.2.1.5 Palladium Nanoparticle Catalysts 253

7.2.2 Stille Coupling 256

7.2.3 Hiyama Coupling 257

7.2.4 Negishi Coupling 259

7.2.5 Sonogashira Coupling 260

7.2.6 Arylation of Other Carbanion Nucleophiles 268

7.2.7 Heck Coupling 270

7.3 Carbon–Heteroatom Coupling Reactions 274

7.3.1 Amination of Aryl Halides 274

7.3.2 Other Carbon–Heteroatom Coupling Reactions 276

7.4 CH Activation in Aqueous Media 277

7.5 Conclusion and Future Prospects 279

Abbreviations 279

References 281

8 Microwave-Assisted Synthesis in CC and Carbon–Heteroatom Coupling Reactions 287
Ke-Hu Wang and Jin-Xian Wang

8.1 Introduction 287

8.2 CC Bond Formation 288

8.2.1 Heck Coupling Reactions 288

8.2.2 Suzuki Reactions 295

8.2.3 Negishi Couplings 308

8.2.4 Coupling of Terminal Alkynes with Aryl Halides 310

8.2.5 Coupling Reactions of Organostannanes with Organic Halides 312

8.2.6 Couplings of Organosilanes with Aryl Halides 313

8.2.7 Cyanation of Aryl Halides 315

8.2.8 Carbonylation Reactions 316

8.2.9 Decarboxylative Couplings 318

8.2.10 Other CC Bond Formations 319

8.3 CX Bond Formation 321

8.3.1 CN Bond Formation 321

8.3.2 CP Bond Formation 325

8.4 Conclusions 327

Abbreviations 327

References 328

9 Catalyst Recycling in Palladium-Catalyzed Carbon–Carbon Coupling Reactions 333
Arpad Molnar

9.1 Introduction 333

9.2 General Issues of Catalyst Recycling 333

9.3 Catalyst Systems Providing High, Consistent Yields in Recycling 337

9.3.1 The Use of Catalysts with Pd Particles 337

9.3.2 Recycling of Palladium Complexes 346

9.3.2.1 Complexes Anchored to Inorganic Supports 346

9.3.2.2 Complexes Immobilized on Polymers 355

9.3.2.3 Self-Supported Polymeric Complexes 361

9.3.3 Studies Performed Under Homogeneous Conditions 362

9.4 Catalysts Affording the Highest Cumulative TON Values in Recycling Studies 370

9.4.1 Catalysts with Supported Particles 370

9.4.2 Immobilized Complexes 373

9.5 Summary Evaluation 375

9.6 Future Outlook 381

Abbreviations 382

References 383

10 Nature of the True Catalytic Species in Carbon–Carbon Coupling Reactions with Heterogeneous Palladium Precatalysts 387
Lin Huang and Pui Kwan Wong

10.1 Introduction 387

10.2 Heck Reactions 389

10.2.1 Supported Pd Particles 389

10.2.2 Immobilized Pd Complexes 394

10.3 Suzuki Reactions 396

10.3.1 Supported Pd Particles 396

10.3.2 Immobilized Pd Complexes 398

10.4 Sonogashira Reactions 402

10.4.1 Supported Pd Particles 402

10.4.2 Immobilized Pd Complexes 403

10.5 Concluding Remarks 404

Abbreviations 406

References 406

11 Coupling Reactions in Continuous-Flow Systems 409
William R. Reynolds and Christopher G. Frost

11.1 Introduction 409

11.2 Coupling Reactions in Flow 410

11.2.1 Suzuki–Miyaura Coupling 410

11.2.2 Mizoroki–Heck Coupling 413

11.2.3 Sonogashira Coupling 415

11.2.4 Murahashi Coupling 416

11.2.5 Hiyama Coupling 418

11.2.6 Carbonylative Couplings 418

11.2.7 Buchwald–Hartwig Amination 420

11.3 Palladium Catalysts for Flow Systems 422

11.3.1 Heterogeneous Supported Catalysts 422

11.3.1.1 Palladium on Charcoal 422

11.3.1.2 Pd EnCat 424

11.3.1.3 Silicon Dioxide Supports 425

11.3.1.4 Polymeric Supports 426

11.3.1.5 Magnetic Nanoparticles 427

11.3.1.6 Monolithic Supports 428

11.3.2 Homogeneous Catalysts 431

11.3.2.1 Single-Phase Reactions 431

11.3.2.2 Biphasic Systems 433

11.4 Continuous-Flow Technologies for Cross-Coupling 435

11.4.1 Microreactors 435

11.4.2 Microwave-Assisted Continuous-Flow Organic Synthesis 436

11.4.3 Toward Sequential Coupling Reactions in Flow 438

11.5 Summary and Outlook 438

Abbreviations 440

References 440

12 Palladium-Catalyzed Cross-Coupling Reactions – Industrial Applications 445
Andreas Dumrath, Christa L€ubbe, and Matthias Beller

12.1 Introduction 445

12.2 Suzuki–Miyaura Reactions 447

12.3 Heck–Mizoroki Reactions 459

12.4 Sonogashira–Hagihara Reactions 463

12.5 Carbonylations 469

12.6 Cyanations 471

12.7 Negishi Coupling 474

12.8 Novel Pd-Catalyzed CC Cross-Coupling Reaction 475

12.9 Buchwald–Hartwig Aminations 475

12.10 Pd-Catalyzed CS Bond Formation 478

12.11 Summary and Outlook 479

Acknowledgments 480

Abbreviations 480

References 481

Index 491

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“This book is an excellent, modern summary of the state of Pd-catalysed coupling reactions. . . This book would be an excellent starting place for an organic chemist who is interested in reducing costs and increasing efficiencies of existing reaction processes or one who is designing new synthetic routes.”  (Platinum Metals Review, 1 March 2014)

“Overall, the sensible and logical presentation of information and breadth of material covered should make this book a very useful interdisciplinary reference text, while also providing for readers seeking an update on the current state of the art in the field palladium cross-coupling chemistry, especially beyond traditional omogeneous catalysed processes.”  (Appl. Organometal. Chem, 1 October 2013)

Note: Product cover images may vary from those shown
Note: Product cover images may vary from those shown

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