Copper-Mediated Cross-Coupling Reactions

Providing comprehensive insight into the use of copper in cross-coupling reactions, Copper-Mediated Cross-Coupling Reactions provides a complete up-to-date collection of the available reactions and catalytic systems for the formation of carbon-heteroatom and carbon-carbon bonds. This essential reference covers a broad scope of copper-mediated reactions, their variations, key advances, improvements, and an array of academic and industrial applications that have revolutionized the field of organic synthesis. The text also discusses the mechanism of these transformations, the use of copper as cost-efficient alternative to palladium, as well as recently developed methods for conducting copper-mediated reactions with supported catalysts.

FOREWORD xvii

Stephen L. Buchwald

PREFACE: COPPER CATALYSIS FROM A HISTORICAL PERSPECTIVE: A LEGACY FROM THE PAST xix

Gwilherm Evano and Nicolas Blanchard

CONTRIBUTORS xxxiii

PART I FORMATION OF C–HETEROATOM BONDS 1

1 Modern Ullmann–Goldberg Chemistry: Arylation of N-Nucleophiles with Aryl Halides 3
Yongwen Jiang and Dawei Ma

1.1 Introduction, 3

1.2 Arylation of Amines, 4

1.3 Arylation of Amides, Imides, and Carbamates, 15

1.4 Arylation of Conjugated N-Heterocycles, 24

1.5 Synthesis of Anilines by Coupling with Ammonia or Synthetic Equivalents, 32

1.6 Conclusion and Future Prospects, 37

References, 37

2 Ullmann Condensation Today: Arylation of Alcohols and Thiols with Aryl Halides 41
Anis Tlili and Marc Taillefer

2.1 Introduction, 41

2.2 Formation of C–O Bonds via Copper-Catalyzed Cross-Coupling Reactions with Aryl Halides, 42

2.3 Formation of C–S Bonds via Copper-Catalyzed Cross-Coupling Reactions with Aryl Halides, 67

2.4 Conclusion, 84

References, 86

3 Copper-Catalyzed Formation of C–P Bonds with Aryl Halides 93
Carole Alayrac and Annie-Claude Gaumont

3.1 Introduction, 93

3.2 Arylation of Phosphines, 94

3.3 Arylation of Phosphine Oxides and Phosphites, 98

3.4 Conclusion, 110

References, 110

4 Alternative and Emerging Reagents for the Arylation of Heteronucleophiles 113
Luc Neuville

4.1 Introduction, 113

4.2 Chan–Lam–Evans Coupling: Copper(II)-Promoted Oxidative Aryl Transfer from Arylboron Derivatives, 115

4.3 Copper-Promoted Aryl Transfer from Metallated Aryl Derivatives (Nonboron), 141

4.4 Copper-Catalyzed Arylation Reactions Involving Masked S- and N-Nucleophiles, 151

4.5 Copper-Catalyzed Direct Heterofunctionalization of Aromatic C–H Bonds, 160

4.6 Conclusion and Future Prospects, 178

References, 178

5 Beyond Ullmann–Goldberg Chemistry: Vinylation, Alkynylation, and Allenylation of Heteronucleophiles 187
Kévin Jouvin and Gwilherm Evano

5.1 Introduction, 187

5.2 Copper-Mediated Alkenylation of Heteronucleophiles: Among the Best Routes to Heteroatom-Substituted Alkenes, 189

5.3 Alkynylation of Heteronucleophiles: The Emergence of General Methods for the Synthesis of Heteroatom-Substituted Alkynes, 219

5.4 Allenylation of Heteronucleophiles: New Tools for the Synthesis of Allenamides, 232

5.5 Conclusion and Future Prospects, 233

References, 234

6 Aromatic/Vinylic Finkelstein Reaction 239
Alicia Casitas and Xavi Ribas

6.1 Introduction, 239

6.2 Copper-Mediated Halogen Exchange Reactions in Aryl Halides, 241

6.3 Most Recent Developments and Overview, 247

References, 249

7 Insights into the Mechanism of Modern Ullmann–Goldberg Coupling Reactions 253
Alicia Casitas and Xavi Ribas

7.1 General View and Key Mechanistic Aspects, 253

7.2 Oxidation State of Copper Catalysts, 254

7.3 Identity of the Active Copper(I) Complex, 255

7.4 Activation Mode of Aryl Halides by Copper Complexes, 261

7.5 Overview, Conclusions, and Future Prospects, 275

References, 277

PART II FORMATION OF C–C BONDS 281

8 Modern Copper-Catalyzed Hurtley Reaction: Efficient C-Arylation of CH-Acid Derivatives 283
Irina P. Beletskaya and Alexey Yu. Fedorov

8.1 Introduction, 283

8.2 Classical Hurtley Reaction, 285

8.3 Ligation Effect in Copper-Catalyzed Reactions of Aryl Halides with Carbanions, 286

8.4 Cascade Reactions Proceeding via a Hurtley Arylation Reaction, 293

8.5 Mechanism of the Copper-Catalyzed C-Arylation Reactions, 303

8.6 Concluding Remarks, 308

References, 308

9 Copper-Catalyzed Cyanations of Aryl Halides and Related Compounds 313
Thomas Schareina and Matthias Beller

9.1 Introduction, 313

9.2 Modifications and Updates of Classical Cyanation Reactions (Rosenmund–von Braun, Sandmeyer), 315

9.3 Copper-Catalyzed Cyanations of Aryl Halides, 316

9.4 Copper-Mediated Oxidative Cyanations, 324

9.5 Conclusion, 331

References, 331

10 Copper-Mediated Aryl–Aryl Bond Formation Leading to Biaryls: A Century after the Ullmann Breakthrough 335
Yoshihiko Yamamoto

10.1 Introduction, 335

10.2 Biaryl Synthesis by Coupling of Aryl Halides and Diazonium Salts, 336

10.3 Biaryl Synthesis by Coupling of Aryltin, Boron, and Silanes, 347

10.4 Biaryl Synthesis by Arylation Involving Arene C–H or C–C Bond Fission, 357

10.5 Biaryl Synthesis by Oxidative Coupling of 2-Naphthols, 376

10.6 Conclusions and Outlook, 387

References, 388

11 Copper-Catalyzed Alkynylation, Alkenylation, and Allylation Reactions of Aryl Derivatives 401
Ren-Jie Song and Jin-Heng Li

11.1 Introduction, 401

11.2 Copper-Catalyzed Alkynylation of Aryl Derivatives, 402

11.3 Copper-Catalyzed Alkenylation of Aryl Derivatives, 432

11.4 Copper-Catalyzed Strategies for the Formation of Allyl–Aryl Bonds, 445

11.5 Conclusion and Outlook, 450

References, 450

12 Copper-Catalyzed Alkynylation and Alkenylation Reactions of Alkynyl Derivatives: New Access to Diynes and Enynes 455
Ruimao Hua

12.1 Introduction, 455

12.2 Copper-Catalyzed Synthesis of Symmetrical and Unsymmetrical 1,3-Diynes, 456

12.3 Copper-Catalyzed Synthesis of 1,4-Diynes, 468

12.4 Synthesis of 1,3-Enynes by Direct Reaction of Vinyl Halides with Alkynes, 468

12.5 Synthesis of 1,3-Enynes by Stille-Type Cross-Coupling Reaction, 474

12.6 Synthesis of 1,3-Enynes by the Suzuki–Miyaura-Type Cross-Coupling Reaction, 476

12.7 Synthesis of 1,4-Enynes by Allylation Reaction of Terminal Alkynes, 478

12.8 Conclusion, 480

References, 480

13 Copper-Mediated Alkenylation Reaction of Alkenyl Derivatives: A Straightforward Elaboration of 1,3-Dienes 485
Hao Li, Songbai Liu, and Lanny S. Liebeskind

13.1 Introduction, 485

13.2 Symmetrical 1,3-Dienes by Homocoupling Reaction of Vinyl Derivatives, 486

13.3 Unsymmetrical 1,3-Dienes by Cross-Coupling Reactions, 496

13.4 Conclusions, 510

References, 511

14 Emerging Areas in Copper-Mediated Trifl uoromethylations of Aryl Derivatives: Catalytic and Oxidative Cross-Coupling Processes 515
Kévin Jouvin, Céline Guissart, Cédric Theunissen, and Gwilherm Evano

14.1 Introduction, 515

14.2 Copper-Catalyzed Trifluoromethylation of Aryl Halides: A Long-Lasting Quest Finally Reached, 517

14.3 Copper-Mediated Oxidative Trifl uoromethylation Reactions, 523

14.4 Conclusion and Future Prospects, 528

References, 528

PART III APPLICATIONS OF COPPER-CATALYZED CROSS-COUPLING REACTIONS: HETEROCYCLES, NATURAL PRODUCTS, PROCESS, AND SUSTAINABLE CHEMISTRY 531

15 Copper-Mediated Cyclization Reactions: New Entries to Heterocycles 533
Daoshan Yang and Hua Fu

15.1 Introduction, 533

15.2 Cyclization by C–N Bond Formation, 534

15.3 Cyclization by C–O Bond Formation, 560

15.4 Cyclization by C–C Bond Formation, 567

15.5 Copper-Catalyzed Double Cross-Coupling Reactions for the Assembly of Heterocycles, 576

15.6 Conclusion and Future Prospects, 583

References, 584

16 Application of Copper-Mediated C–N Bond Formation in Complex Molecules Synthesis 589
Jihoon Lee and James S. Panek

16.1 Introduction, 589

16.2 Aryl Amination in Complex Molecule Synthesis, 590

16.3 Aryl Amidation in Complex Molecule Synthesis, 595

16.4 Arylation of N-Heterocycles in Complex Molecule Synthesis, 601

16.5 Vinyl Amidation in Complex Molecule Synthesis, 606

16.6 Alkyne Amidation in Complex Molecule Synthesis, 620

16.7 Intramolecular C–N Bond Formation in Natural Product Synthesis, 622

16.8 Summary and Outlook, 637

References, 638

17 Natural Products and C–O/C–S Bond-Forming Reactions: Copper Showed the Way 643
Doron Pappo

17.1 Introduction, 643

17.2 Total Synthesis of Naturally Occurring Diaryl Ethers by Arylation of Phenols, 644

17.3 Intramolecular Diaryl Ether Bond-Forming Reactions, 659

17.4 Arylation of Alcohols, 666

17.5 Vinylation of Alcohols, 673

17.6 Copper-Mediated C–S Bond Formation in Natural Product Synthesis, 675

17.7 Conclusion and Future Prospects, 677

References, 678

18 Copper-Catalyzed C–C Bond Formation in Natural Product Synthesis: Elegant and Efficient Solutions to a Key Bond Disconnection 683
Morgan Donnard and Nicolas Blanchard

18.1 Introduction, 683

18.2 Natural Biaryls by Copper-Catalyzed Cross Coupling, 684

18.3 Copper-Catalyzed 1,3-Enyne Formation, 691

18.4 Copper-Mediated Synthesis of Dienes, Trienes, and Extended Polyenes, 694

18.5 Copper-Catalyzed Synthesis of 1,N-Polyynes Natural Products, 711

18.6 Conclusions and Future Prospects, 718

References, 719

19 Process Chemistry and Copper Catalysis 725
Klaus Kunz and Norbert Lui

19.1 Introduction and Scope, 725

19.2 Copper versus Palladium, 727

19.3 Applications, 727

19.4 Conclusion, 739

References, 740

20 Reusable Catalysts for Copper-Mediated Cross-Coupling Reactions under Heterogeneous Conditions 745
Zhiyong Wang, Changfeng Wan, and Ye Wang

20.1 Introduction, 745

20.2 Copper Nanoparticle-Catalyzed Cross-Coupling Reactions, 746

20.3 Supported Copper-Catalyzed Cross-Coupling Reaction, 766

20.4 Conclusion, 780

References, 780

INDEX 785

GWILHERM EVANO is a Professor at the Université Libre de Bruxelles and the Co-Director of the Laboratory of Organic Chemistry. Prof. Evano's research focuses on the development of copper-mediated transformations, chemistry of ynamides and other hetero-substituted alkynes, and total synthesis of natural products.

NICOLAS BLANCHARD is Research Director at the French National Center for Scientific Research at the University of Strasbourg. Dr. Blanchard's research interests focus on the synthesis of biologically relevant compounds using metal-mediated transformations.