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Copper Catalysis in Organic Synthesis. Edition No. 1

  • ID: 5185428
  • Book
  • October 2020
  • 504 Pages
  • John Wiley and Sons Ltd
The most current information on growing field of copper catalysis

Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors?noted experts on the topic?provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C?H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions.

Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: - Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry - Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions - Presents the most significant developments in the area, including cross-coupling reactions, C?H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles - Contains over 20 contributions from leaders in the field

Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C?H activation, and applications in the total synthesis of natural products.
Note: Product cover images may vary from those shown

Preface xvii

Abbreviations xix

1 Copper Catalysis: An Introduction 1
Salim Saranya and Gopinathan Anilkumar

References 4

2 Cu-Catalyst in Reactions Involving Pyridinium and Indolizinium Moieties 7
Bianca Furdui, Andrea V. Dediu (Botezatu), and RodicaM. Dinica

2.1 Cu-Catalyst in Reactions Involving Pyridinium Moieties 7

2.1.1 Introduction 7

2.1.2 Synthesis and Functionalization of Pyridinium Compounds Catalyzed by Copper 7

2.1.3 Green Methods for Pyridine Synthesis 13

2.2 Cu-Catalyst in Reactions Involving Indolizinium Moieties 15

2.2.1 Introduction 15

2.2.2 Synthesis of Indolizinium Compounds Using a Copper Catalyst 15

2.2.3 Cu-Catalyzed Green Synthesis of Indolizine Moieties 19

2.3 Conclusions 21

References 21

3 Copper-Catalyzed Cross-Coupling Reactions of Organoboron Compounds 23
Jan Nekvinda and Webster L. Santos

3.1 Introduction 23

3.2 Ring Opening Cross-Coupling Reactions 24

3.3 Coupling Reactions with Atoms Other than Carbon 26

3.3.1 Amines, Amides, and Sulfonamides 27

3.3.2 Nitrones 33

3.3.3 Sulfones 35

3.3.4 Silyls 35

3.3.5 Selanyls 36

3.4 Coupling Reactions Involving Carbon 36

3.4.1 Boronic Acid Esters 36

3.4.2 Boronic Acids 41

3.4.3 Single Electron Mechanism 42

3.5 Conclusion 43

References 43

4 Cu-Catalyzed Homocoupling Reactions 51
Ganesh C. Nandi, Sundaresan Ravindra, Cholakkaparambil Irfana Jesin, Parameswaran Sasikumar, and Kokkuvayil V. Radhakrishnan

4.1 Introduction 51

4.2 Synthesis of 1,3-Diynes via Homocoupling Reactions 51

4.2.1 Synthesis of 1,3-Diynes with Homogeneous Cu Catalysis 52

4.2.1.1 Synthesis of Symmetrical 1,3-Diynes with Substrates Other than Terminal Alkynes 54

4.2.2 Synthesis of Symmetrical 1,3-Diynes with Heterogeneous Cu Catalysis 55

4.2.3 Synthesis of Macrocycles Through Intramolecular Coupling of Terminal Alkynes 56

4.3 Cu-Catalyzed Synthesis of Symmetrical Biaryls Through Homocoupling Reactions 57

4.3.1 Homocoupling of Aryl Boronic Acids 58

4.3.1.1 Homogeneous Cu-Catalyzed Homocoupling Reactions 58

4.3.1.2 Heterogeneous Copper-Catalyzed Homocoupling Reactions 58

4.3.2 Synthesis of Symmetrical Biaryls Through C–H Activation 59

4.3.3 Homocoupling of Arylstannane/Silane Derivatives 62

4.3.4 Cu-Catalyzed Homocoupling of Aryl Halides for the Synthesis of Biaryls 62

4.3.4.1 Symmetrical Biaryl Formation Using Homogeneous Copper Catalyst 62

4.3.4.2 Biaryl Formation Using Heterogeneous Cu Catalyst 65

4.3.5 Cu-Catalyzed Homocoupling of Aryl Halides for the Formation of Biaryls in Natural Products 66

4.4 Homocoupling of Alkenes 68

4.5 Summary and Conclusions 69

References 69

5 Cu-Catalyzed Organic Reactions in Aqueous Media 73
Noel Nebra and Joaquín García-Álvarez

5.1 Introduction 73

5.2 Cu-Catalyzed Azide–Alkyne Cycloaddition Reactions (CuAAC) 74

5.2.1 Ligand-Accelerated Cu(I) Catalysts 74

5.2.2 Supported Cu(I) Catalysts 75

5.2.3 Micellar Cu(I) Catalysis 77

5.2.4 Heterogeneous Catalysis: CuNPs 77

5.2.5 Miscellaneous 80

5.3 Cu-Mediated Cross-Coupling Reactions: C - C and C–Heteroatom Bond Formation 81

5.3.1 The Ullmann Coupling 81

5.3.2 The Chan–Lam–Evans (CEL) Coupling 83

5.3.3 Cu-Catalyzed Cyclization Reactions via Cross-Coupling Events 85

5.3.4 Cu-Catalyzed C - H Bond Functionalization Reactions 86

5.4 Cu-Catalyzed Hydroelementation Reactions of Double and Triple C - C Bonds 89

5.4.1 Michael-Type Additions: Enone Hydrations Enabled by Cu-Based Metallo-Hydratases 89

5.4.2 Cu-Catalyzed Hydroelementation of α,β-Unsaturated Carbonyl Compounds 90

5.4.3 Cu-Catalyzed Hydroelementation of Inactivated C - C Multiple Bonds 92

5.5 Miscellaneous 96

5.6 Summary and Conclusions 98

Acknowledgments 98

References 100

6 Cu-Catalyzed Organic Reactions in Deep Eutectic Solvents (DESs) 103
Noel Nebra and Joaquín García-Álvarez

6.1 Introduction 103

6.2 Cu-Catalyzed Azide–Alkyne Cycloaddition Reactions (CuAAC) in DESs 106

6.3 Cu-Catalyzed C - C and C - N Bond Formations in DESs 108

6.3.1 Cu-Catalyzed Sonogashira C–C Coupling Using the Eutectic Mixture 1CuCl/1Gly 108

6.3.2 Synthesis of Heterocyclic Compounds via Cu-Catalyzed Cross-Coupling Reactions 110

6.3.3 Cu-Catalyzed C - N Bond Formation in DESs 110

6.4 Cu-Catalyzed Atom Transfer Radical Polymerization Processes in DESs (SARA and ARGET) 112

6.5 Summary and Conclusions 113

Acknowledgments 114

References 114

7 Microwave-Assisted Cu-Catalyzed Organic Reactions 119
Bogdan Štefane, Helena Brodnik-Žugelj, Uroš Grošelj, Jurij Svete, and Franc Požgan

7.1 Introduction 119

7.2 Ring-Forming Reactions 121

7.2.1 Synthesis of Heterocycles 121

7.2.1.1 Cycloadditions 121

7.2.1.2 Annulation Reactions 123

7.2.1.3 Intramolecular Cyclizations 126

7.2.1.4 Multicomponent Reactions (MCRs) 126

7.2.2 Synthesis of Carbocycles 128

7.3 Cross-Coupling Reactions 130

7.3.1 Carbon–Carbon Couplings 130

7.3.2 Carbon–Heteroatom Couplings 134

7.3.2.1 C–N Couplings 134

7.3.2.2 C–Chalcogen Couplings 138

7.4 Multicomponent Reactions 141

7.5 Miscellaneous Reactions 144

7.6 Summary and Conclusions 146

Acknowledgments 146

References 146

8 Cu-Catalyzed Asymmetric Synthesis 153
Hidetoshi Noda, Naoya Kumagai, and Masakatsu Shibasaki

8.1 Introduction 153

8.1.1 Cu-Catalyzed Asymmetric Synthesis: Scope of This Chapter 153

8.1.2 Structures of Chiral Ligands: Trends of the Last Decade 154

8.2 In Situ Generation of Cu Nucleophiles from Unsaturated Hydrocarbons 155

8.2.1 Reductive Aldol Reactions 155

8.2.2 Intramolecular Oxy- and Amidocupration 156

8.2.3 Hydrocupration of Unsaturated Compounds 158

8.2.4 Borylcupuration of Unsaturated Compounds 163

8.3 Generation of Cu Nucleophiles Under Proton Transfer Conditions 165

8.4 Summary and Conclusions 172

References 172

9 Cu-Catalyzed Click Reactions 177
Rajagopal Ramkumar and Pazhamalai Anbarasan

9.1 Introduction 177

9.2 Background 178

9.2.1 Huisgen’s Cycloaddition Reaction 178

9.2.2 Copper(I)-Catalyzed Azide–Alkyne Cycloaddition (CuAAC) 178

9.2.3 Mechanistic Study of Copper Azide–Alkyne Cycloaddition Reaction 179

9.3 CuAAC for the Synthesis of Substituted 1,2,3-Triazoles 180

9.4 Heterogeneous CuAAC Reactions 188

9.5 Ligand-Stabilized Cu(I)-Catalyzed Click Reaction 191

9.6 Synthesis of Rotaxanes and Catenanes Using CuAAC 196

9.7 Synthesis of N-Sulfonyl-1,2,3-Triazoles and Their Applications 198

9.8 CuAAC and Asymmetric Synthesis 198

9.9 CuAAC for Synthesis of Biologically Active Molecules 202

9.10 Summary 204

References 204

10 Cu-Catalyzed Multicomponent Reactions 209
Thachapully D. Suja and Rajeev S. Menon

10.1 Introduction 209

10.2 Cu-Catalyzed MCRs of Alkynes 209

10.2.1 Cu-Catalyzed Multicomponent Alkyne–Azide Cycloadditions 210

10.2.1.1 CuAAC Reactions Initiated by Azide Generation 210

10.2.1.2 CuAAC Reactions Initiated by Alkyne Generation 214

10.2.1.3 Other Multicomponent CuAAC Reactions 214

10.2.2 Cu-Catalyzed Generation and Interception of Ketenimines from Alkynes and Azides 216

10.2.3 Cu-Catalyzed Aldehyde, Alkyne, and Amine (A3) Coupling 221

10.2.3.1 A3-Coupling ReactionsThat Afford Propargyl Amine Derivatives 222

10.2.3.2 Variation of the Reaction Components in A3-Coupling 224

10.2.3.3 Asymmetric A3 (AA3)-Coupling Reactions 226

10.2.3.4 Synthetic Applications of Cu-Catalyzed A3-Coupling Reactions 227

10.3 Other Cu-Catalyzed Multicomponent Reactions 229

10.4 Summary and Conclusions 233

References 233

11 Copper-Catalyzed Aminations 239
Nissy A. Harry and Rajenahally V. Jagadeesh

11.1 Introduction 239

11.2 Copper-Catalyzed Amination of Aryl and Alkenyl Electrophiles 240

11.2.1 Ammonia as a Nucleophile 240

11.2.2 Sodium Azide as Nucleophile 241

11.2.3 Amines as Nucleophile 242

11.2.4 Mechanism of Cu-Catalyzed Amination of Aryl/Alkyl Halides 244

11.3 Chan–Lam Coupling Reaction 244

11.4 Copper-Catalyzed Hydroaminations 246

11.4.1 Hydroamination of Alkenes 247

11.4.2 Hydroamination of Alkynes 250

11.4.3 Hydroamination of Allenes 251

11.5 Copper-Catalyzed C - H amination Reactions 251

11.6 Conclusion 254

References 254

12 Cu-Catalyzed Carbonylation Reactions 261
Parameswaran Sasikumar, Thoppe S. Priyadarshini, Sanjay Varma, Ganesh C. Nandi, and Kokkuvayil V. Radhakrishnan

12.1 Introduction 261

12.2 Single Carbonylation Reactions 262

12.2.1 Copper-Catalyzed Carbonylative Coupling Reactions 262

12.2.2 Cu-Catalyzed Carboxylation Reaction 268

12.2.3 Cu-Catalyzed Oxidative Carbonylation Reactions 269

12.2.4 Carbonylative Acetylation Reaction 272

12.2.5 Aminocarbonylation Reaction 273

12.2.6 Copper-Catalyzed Oxidative Amidation 275

12.3 Cu-Catalyzed Double Carbonylation Reactions 275

12.4 Summary and Conclusions 278

References 278

13 Ligand-Free, Cu-Catalyzed Reactions 279
Muhammad F. Jamali, Sanoop P. Chandrasekharan, and Kishor Mohanan

13.1 Introduction 279

13.2 Heterocycle Synthesis 279

13.2.1 Five-Membered Heterocycles 280

13.2.2 Six-Membered Heterocycles 280

13.2.3 Benzofused Five-Membered Heterocycles Containing One Heteroatom 281

13.2.4 Benzofused Five-Membered Heterocycles Containing Two Heteroatoms 283

13.2.5 Benzofused Five-Membered Heterocycles Containing Three Heteroatoms 284

13.2.6 Benzofused Six-Membered Heterocycles 284

13.2.7 Polycyclic Compounds 286

13.2.8 Spirocyclic Compounds 286

13.3 Carbon–Heteroatom Bond Formations 289

13.3.1 C - N Bond Formation 289

13.3.2 C - O Bond Formation 291

13.3.3 C - S Bond Formation 291

13.3.4 C - P Bond Formation 295

13.3.5 C - B Bond Formation 295

13.3.6 C - Se Bond Formation 295

13.4 C–H Activation Reactions 297

13.5 Cross-coupling Reactions 299

13.6 Azide–Alkyne Cycloaddition Reactions (CuAAC) 301

13.7 Trifluoromethylation Reactions 302

13.8 Cyanation Reactions 303

13.9 Carbonylation Reactions 304

13.10 Conclusion 305

References 305

14 Copper-Catalyzed Decarboxylative Coupling 309
Firas El-Hage and Jola Pospech

14.1 Introduction 309

14.2 Copper-Catalyzed Decarboxylation of Benzoic Acids 309

14.3 Copper-Catalyzed Decarboxylation of Alkenyl Carboxylic Acids 315

14.4 Copper-Catalyzed Decarboxylation of Alkynyl Carboxylic Acids 316

14.5 Copper-Catalyzed Decarboxylation of Alkyl Carboxylic Acids 320

14.6 Summary and Conclusions 325

References 326

15 Copper-Catalyzed C–H Activation 329
Xun-Xiang Guo

15.1 Introduction 329

15.2 Carbon–Carbon Bond Formation via Cu-Catalyzed C–H Activation 329

15.2.1 Cu-Catalyzed C(sp2)–H Activation 329

15.2.2 Cu-Catalyzed C(sp3)–H Activation 332

15.3 Carbon–Heteroatom Bond Formation via Cu-Catalyzed C–H Activation 334

15.3.1 C - N Bond Formation 334

15.3.2 C - O Bond Formation 339

15.3.3 C - X Bond Formation 341

15.3.4 C - P Bond Formation 345

15.3.5 C - S Bond Formation 346

15.4 Conclusion 347

References 347

16 Aerobic Cu-Catalyzed Organic Reactions 349
Ahmad A. Almasalma and Esteban Mejía

16.1 Introduction 349

16.2 C - C Bond Formation Reactions 351

16.2.1 Cross-dehydrogenative Couplings Under Thermal Conditions 352

16.2.2 Cross-dehydrogenative Couplings Under Photochemical Conditions 354

16.3 Carbonyl Synthesis via Oxidation of Alcohols 357

16.3.1 “Copper-Only” Biomimetic Catalyst Systems 358

16.3.2 Cu/Nitroxyl “Dual” Systems 360

16.4 Summary and Conclusions 362

References 363

17 Copper-Catalyzed Trifluoromethylation Reactions 367
Dzmitry G. Kananovich

17.1 Introduction 367

17.2 Trifluoromethylation of Arenes and Heteroarenes (C(sp2) - CF3 Bond Formation) 370

17.3 Trifluoromethylation of Alkenes and Alkynes 374

17.4 Trifluoromethylation of Aliphatic Precursors (C(sp3) - CF3 Bond Formation) 378

17.4.1 Transformations via Functional Group Interconversions 378

17.4.2 Direct C(sp3)–H Trifluoromethylation 382

17.4.3 Ring-opening Trifluoromethylation 386

17.5 Copper-Mediated Formation of CF3–Heteroatom Bonds 388

17.6 Summary and Conclusions 388

References 389

18 Cu-Catalyzed Reactions for Carbon–Heteroatom Bond Formations 395
Govindasamy Sekar, Subramani Sangeetha, Anuradha Nandy, and Rajib Saha

18.1 Introduction 395

18.2 Cu-Catalyzed Reactions for Carbon–Nitrogen Bond Formations 395

18.2.1 Coupling Reactions with Ammonia and its Surrogates 396

18.2.2 Coupling Reactions with Amines 396

18.2.3 Coupling Reactions with Amides, Lactams, and Carbamates 398

18.2.4 Coupling Reactions with Protected Hydrazines and Hydroxylamines 400

18.2.5 Coupling Reactions with Guanidines 400

18.2.6 Coupling Reactions with N-Heterocycles 401

18.3 Cu-Catalyzed Reactions for Carbon–Oxygen Bond Formations 401

18.3.1 Mechanism and Presence of Cu(I) Intermediate in Ullmann Ether Synthesis 402

18.3.2 Role of Ligands in Copper-Catalyzed Ether Synthesis 403

18.3.3 Copper-Catalyzed C - O Bond Formation for Synthesizing Phenols 404

18.3.4 Copper-Catalyzed C - H Functionalization for C - O Bond Formation 405

18.3.5 Copper-Catalyzed Synthesis of Oxygen Heterocycles 405

18.3.6 Selectivity of Copper-Catalyzed C - O and C - N Bond Formation 406

18.4 Cu-Catalyzed Reactions for Carbon–Sulfur Bond Formations 407

18.5 Cu-Catalyzed Reactions for Carbon–Selenium and Carbon–Tellurium Bond Formations 413

18.6 Cu-Catalyzed Reactions for Carbon–Phosphorous Bond Formations 414

18.7 Cu-Catalyzed Reactions for Carbon–Silicon Bond Formations 415

18.8 Cu-Catalyzed Reactions for Carbon–Halogen Bond Formations 415

18.9 Conclusions 416

References 416

19 Cu-Assisted Cyanation Reactions 423
Sumanta Garai and Ganesh A. Thakur

19.1 Introduction 423

19.2 Cyanation Reaction Using CN-Containing Source 423

19.2.1 Metallic Bound CN-Source 423

19.2.1.1 Metal Cyanide 423

19.2.1.2 Potassium Ferrocyanide [K3Fe(CN)6] 427

19.2.2 Nonmetallic CN-Source 427

19.2.2.1 Acetone Cyanohydrin 427

19.2.2.2 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) 428

19.2.2.3 2,2′-Azobisisobutyronitrile (AIBN) 429

19.2.2.4 Benzyl Cyanide 429

19.2.2.5 Acetonitrile 432

19.2.2.6 Malononitrile 435

19.2.2.7 Cyanogen Iodide 436

19.2.2.8 α-Cyanoacetate 436

19.3 Cyanation Reaction Using Non-CN-Containing Source 437

19.3.1 N,N-Dimethylformamide (DMF) 437

19.3.2 Ammonium Iodide (NH4I) and N,N-Dimethylformamide (DMF) 439

19.3.3 Nitromethane 441

Acknowledgments 441

References 441

20 Application of Cu-Mediated Reactions in the Synthesis of Natural Products 443
Anas Ansari and Ramesh Ramapanicker

20.1 Introduction 443

20.2 Classification 443

20.3 Total Synthesis Employing Cu-Catalyzed C–C Coupling Reactions 445

20.3.1 (+)-Nocardioazine B 445

20.3.2 (−)-Rhazinilam 447

20.3.3 Isohericenone and Erinacerin A 447

20.3.4 (+)-Piperarborenine B 449

20.3.5 Macrocarpines D and E 450

20.4 Total Synthesis Employing Cu-Catalyzed C–N Coupling Reactions 454

20.4.1 (−)-Aspergilazine A 454

20.4.2 (−)-Psychotriasine 454

20.4.3 (−)-Indolactam V 455

20.4.4 (−)-Palmyrolide A 458

20.5 Total Synthesis Employing Cu-Catalyzed C–O Coupling Reactions 458

20.5.1 (±})-Untenone A 458

20.5.2 Coumestrol and Aureol 460

20.6 Total Synthesis Employing Cu-Catalyzed Domino Reactions 463

20.6.1 (±})-Sacidumlignan D 463

20.7 Conclusion 463

References 465

Index 469

Note: Product cover images may vary from those shown
Gopinathan Anilkumar
Salim Saranya
Note: Product cover images may vary from those shown
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