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Catalytic Cascade Reactions

Peng-Fei Xu (Editor), Wei Wang (Editor)
ISBN: 978-1-118-01602-2
440 pages
November 2013
Catalytic Cascade Reactions (1118016025) cover image

Demonstrates the advantages of catalytic cascade reactions for synthesizing natural products and pharmaceuticals

Riding the wave of green chemistry, catalytic cascade reactions have become one of the most active research areas in organic synthesis. During a cascade reaction, just one reaction solvent, one workup procedure, and one purification step are needed, thus significantly increasing synthetic efficiency.

Featuring contributions from an international team of pioneers in the field, Catalytic Cascade Reactions demonstrates the versatility and application of these reactions for synthesizing valuable compounds. The book examines both organocatalysis and transition-metal catalysis reactions, bringing readers up to date with the latest discoveries and activities in all major areas of catalytic cascade reaction research.

Catalytic Cascade Reactions begins with three chapters dedicated to organocatalytic cascade reactions, exploring amines, Brønsted acids, and the application of organocatalytic cascade reactions in natural product synthesis and drug discovery. Next, the book covers:

  • Gold-catalyzed cascade reactions
  • Cascade reactions catalyzed by ruthenium, iron, iridium, rhodium, and copper
  • Palladium-catalyzed cascade reactions of alkenes, alkynes, and allenes
  • Application of transition-metal catalyzed cascade reactions in natural product synthesis and drug discovery
  • Engineering mono- and multifunctional nanocatalysts for cascade reactions
  • Multiple-catalyst-promoted cascade reactions

All chapters are thoroughly referenced, providing quick access to important original research findings and reviews so that readers can explore individual topics in greater depth.

Drawing together and analyzing published findings scattered across the literature, this book provides a single source that encapsulates our current understanding of catalytic cascade processes. Moreover, it sets the stage for the development of new catalytic cascade reactions and their applications.

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Contributors xi

Preface xiii

1 Amine-Catalyzed Cascade Reactions 1
Aiguo Song and Wei Wang

1.1 Introduction, 2

1.2 Enamine-Activated Cascade Reactions, 3

1.2.1 Enamine–Enamine Cascades, 3

1.2.2 Enamine–Iminium Cascades, 8

1.2.3 Enamine Catalysis Cyclization, 19

1.3 Iminium-Initiated Cascade Reactions, 21

1.3.1 Design of Iminium–Enamine Cascade Reactions, 21

1.3.2 Iminium-Activated Diels–Alder Reactions, 22

1.3.3 Iminium-Activated Sequential [4 + 2] Reactions, 24

1.3.4 Iminium-Activated [3 + 2] Reactions, 25

1.3.5 Iminium-Activated Sequential [3 + 2] Reactions, 27

1.3.6 Iminium-Activated [2 + 1] Reactions, 30

1.3.7 Iminium-Activated Multicomponent Reactions, 35

1.3.8 Iminium-Activated [3 + 3] Reactions, 37

1.4 Cycle-Specific Catalysis Cascades, 42

1.5 Other Strategies, 45

1.6 Summary and Outlook, 46

References, 46

2 Brønsted Acid–Catalyzed Cascade Reactions 53
Jun Jiang and Liu-Zhu Gong

2.1 Introduction, 54

2.2 Protonic Acid–Catalyzed Cascade Reactions, 55

2.2.1 Mannich Reaction, 55

2.2.2 Pictect–Spengler Reaction, 56

2.2.3 Biginelli Reaction, 58

2.2.4 Povarov Reaction, 59

2.2.5 Reduction Reaction, 60

2.2.6 1,3-Dipolar Cycloaddition, 61

2.2.7 Darzen Reaction, 65

2.2.8 Acyclic Aminal and Hemiaminal Synthesis, 66

2.2.9 Rearrangement Reaction, 67

2.2.10 a,b-Unsaturated Imine-Involved Cyclization Reaction, 69

2.2.11 Alkylation Reaction, 69

2.2.12 Desymmetrization Reaction, 70

2.2.13 Halocyclization, 71

2.2.14 Redox Reaction, 72

2.2.15 Isocyanide-Involved Multicomponent Reaction, 73

2.2.16 Other Protonic Acid–Catalyzed Cascade Reactions, 75

2.3 Chiral Thiourea (Urea)–Catalyzed Cascade Reactions, 75

2.3.1 Neutral Activation, 76

2.3.2 Anion-Binding Catalysis, 99

2.4 Brønsted Acid and Transition Metal Cooperatively Catalyzed Cascade Reactions, 104

2.4.1 Dual Catalysis, 105

2.4.2 Cascade Catalysis, 108

2.5 Conclusions, 116

References, 117

3 Application of Organocatalytic Cascade Reactions in Natural Product Synthesis and Drug Discovery 123
Yao Wang and Peng-Fei Xu

3.1 Introduction, 123

3.2 Amine-Catalyzed Cascade Reactions in Natural Product Synthesis, 125

3.2.1 Iminium-Ion-Catalyzed Cascade Reactions in Natural Product Synthesis, 125

3.2.2 Cycle-Specific Cascade Catalysis in Natural Product Synthesis, 129

3.3 Brønsted Acid–Catalyzed Cascade Reactions in Natural Product Synthesis, 137

3.4 Bifunctional Base/Brønsted Acid–Catalyzed Cascade Reactions in Natural Product Synthesis, 139

3.5 Summary and Outlook, 140

References, 142

4 Gold-Catalyzed Cascade Reactions 145
Yanzhao Wang and Liming Zhang

4.1 Introduction, 145

4.2 Cascade Reactions of Alkynes, 147

4.2.1 Cascade Reactions of Enynes, 147

4.2.2 Cascade Reactions of Propargyl Carboxylates, 156

4.2.3 Cascade Reactions of ortho-Substituted Arylalkynes, 161

4.2.4 Cascade Reactions of Other Alkynes, 165

4.3 Cascade Reactions of Allenes, 170

4.4 Cascade Reactions of Alkenes and Cyclopropenes, 173

4.5 Closing Remarks, 174

References, 174

5 Cascade Reactions Catalyzed by Ruthenium, Iron, Iridium, Rhodium, and Copper 179
Yanguang Wang and Ping Lu

5.1 Introduction, 179

5.2 Ruthenium-Catalyzed Transformations, 180

5.3 Iron-Catalyzed Transformations, 185

5.4 Iridium-Catalyzed Transformations, 191

5.5 Rhodium-Catalyzed Transformations, 194

5.6 Copper-Catalyzed Transformations, 202

5.7 Miscellaneous Catalytic Reactions, 215

5.8 Summary, 219

References, 219

6 Palladium-Catalyzed Cascade Reactions of Alkenes, Alkynes, and Allenes 225
Hongyin Gao and Junliang Zhang

6.1 Introduction, 226

6.2 Cascade Reactions Involving Alkenes, 226

6.2.1 Double Mizoroki–Heck Reaction Cascade, 226

6.2.2 Cascade Heck Reaction/C-H Activation, 227

6.2.3 Cascade Heck Reaction/Reduction/Cyclization, 230

6.2.4 Cascade Heck Reaction/Carbonylation, 231

6.2.5 Cascade Heck Reaction/Suzuki Coupling, 232

6.2.6 Cascade Amino-/Oxopalladation/Carbopalladation Reaction, 234

6.3 Cascade Reactions Involving Alkynes, 237

6.3.1 Cascade Heck Reactions, 238

6.3.2 Cascade Heck/Suzuki Coupling, 238

6.3.3 Cationic Palladium(II)-Catalyzed Cascade Reactions, 239

6.3.4 Cascade Heck Reaction/Stille Coupling, 241

6.3.5 Cascade Heck/Sonogashira Coupling, 243

6.3.6 Cascade Sonogashira Coupling–Cyclization, 244

6.3.7 Cascade Heck and C-H Bond Functionalization, 247

6.3.8 Cascade Reactions Initiated by Oxopalladation, 253

6.3.9 Cascade Reactions Initiated by Aminopalladation, 256

6.3.10 Cascade Reactions Initiated by Halopalladation or Acetoxypalladation, 259

6.3.11 Cascade Reactions of 2-(1-Alkynyl)-alk-2-en-1-ones, 263

6.3.12 Cascade Reactions of Propargylic Derivatives, 263

6.4 Cascade Reactions Involving Allenes, 264

6.4.1 Cascade Reactions of Monoallenes, 264

6.4.2 Cross-Coupling Cyclization of Two Different Allenes, 274

6.5 Summary and Outlook, 276

Acknowledgments, 277

References, 277

7 Use of Transition Metal–Catalyzed Cascade Reactions in Natural Product Synthesis and Drug Discovery 283
Peng-Fei Xu and Hao Wei

7.1 Introduction, 283

7.2 Palladium-Catalyzed Cascade Reactions in Total Synthesis, 284

7.2.1 Cross-Coupling Reactions, 284

7.2.1.1 Heck Reaction, 284

7.2.1.2 Stille Reaction, 291

7.2.1.3 Suzuki Coupling Reaction, 297

7.2.2 Tsuji–Trost Reaction, 301

7.2.3 Other Palladium-Catalyzed Cascade Reactions in Total Synthesis, 303

7.3 Ruthenium-Catalyzed Cascade Reactions in Total Synthesis, 305

7.4 Gold-and Platinum-Catalyzed Cascade Reactions in Organic Reactions, 318

7.5 Copper-and Rhodium-Catalyzed Cascade Reactions in Organic Synthesis, 322

7.6 Summary, 326

References, 326

8 Engineering Mono-and Multifunctional Nanocatalysts for Cascade Reactions 333
Hexing Li and Fang Zhang

8.1 Introduction, 334

8.2 Heterogeneous Monofunctional Nanocatalysts, 335

8.2.1 Metal-Based Monofunctional Nanocatalysts, 335

8.2.2 Metal Oxide–Based Monofunctional Nanocatalysts, 340

8.2.3 Orgamometallic-Based Monofunctional Nanocatalysts, 340

8.2.4 Graphene Oxide–Based Monofunctional Nanocatalysts, 343

8.3 Heterogeneous Multifunctional Nanocatalysts, 344

8.3.1 Acid–Base Combined Multifunctional Nanocatalysts, 344

8.3.2 Metal–Base Combined Multifunctional Nanocatalysts, 349

8.3.3 Organometallic–Base Combined Multifunctional Nanocatalysts, 349

8.3.4 Binary Organometallic–Based Multifunctional Nanocatalysts, 350

8.3.5 Binary Metal–Based Multifunctional Nanocatalysts, 352

8.3.6 Metal–Metal Oxide Combined Multifunctional Nanocatalysts, 353

8.3.7 Organocatalyst–Acid Combined Multifunctional Nanocatalysts, 353

8.3.8 Acid–Base–Metal Combined Multifunctional Nanocatalyst, 356

8.3.9 Triple Enzyme–Based Multifunctional Nanocatalysts, 356

8.4 Conclusions and Perspectives, 359

References, 360

9 Multiple-Catalyst-Promoted Cascade Reactions 363
Peng-Fei Xu and Jun-Bing Ling

9.1 Introduction, 363

9.2 Multiple Metal Catalyst–Promoted Cascade Reactions, 364

9.2.1 Catalytic Systems Involving Palladium, 365

9.2.2 Catalytic Systems Involving Other Metals, 368

9.3 Multiple Organocatalyst–Promoted Cascade Reactions, 370

9.3.1 Catalytic Systems Combining Multiple Amine Catalysts, 371

9.3.2 Catalytic Systems Combining Amine Catalysts and Nucleophilic Carbenes, 380

9.3.3 Catalytic Systems Combining Amine and Hydrogen-Bonding Donor Catalysts, 385

9.3.4 Catalytic Systems Involving Other Organocatalysts, 390

9.4 Metal/Organic Binary Catalytic System–Promoted Cascade Reactions, 394

9.4.1 Catalytic Systems Combining Secondary Amine and Metal Catalysts, 394

9.4.2 Catalytic Systems Combining Brønsted Acid and Metal Catalysts, 404

9.4.3 Catalytic Systems Combining Hydrogen-Bonding Donor and Metal Catalysts, 411

9.4.4 Catalytic Systems Combining Other Organo-and Metal Catalysts, 413

9.5 Summary and Outlook, 415

References, 415

Index 419

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PENG-FEI XU, PhD, is Director of Teaching Affairs and Professor of Chemistry at Lanzhou University and Deputy Director at the State Key Laboratory of Applied Organic Chemistry. Dr. Xu also serves as an Advisory Board member for the Chinese Chemical Society. During his scientific career, he has published more than 130 papers and received numerous honors and awards, most recently the Award of New Century Excellent Talents in Universities of China and the Thieme Journal Award.

WEI WANG, PhD, is Professor of Chemistry at the University of New Mexico. Dr. Wang has published more than 160 peer-reviewed papers. He has received several awards, including The Creative Award from University of New Mexico, The Chinese-American Chemistry & Chemical Biology Professors Association Distinguished Junior Faculty Award, and The American Peptide Society Bruce W. Erickson Young Investigator Award.

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