Description
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. GWILHERM EVANO is a Professor at the Universit 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. 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 Kvin 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 Kvin Jouvin, Cline Guissart, Cdric 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
