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 xviiStephen L. BuchwaldPREFACE: COPPER CATALYSIS FROM A HISTORICAL PERSPECTIVE: A LEGACY FROM THE PAST xixGwilherm Evano and Nicolas BlanchardCONTRIBUTORS xxxiiiPART I FORMATION OF C-HETEROATOM BONDS 11 Modern Ullmann-Goldberg Chemistry: Arylation of N-Nucleophiles with Aryl Halides 3Yongwen Jiang and Dawei Ma1.1 Introduction, 31.2 Arylation of Amines, 41.3 Arylation of Amides, Imides, and Carbamates, 151.4 Arylation of Conjugated N-Heterocycles, 241.5 Synthesis of Anilines by Coupling with Ammonia or Synthetic Equivalents, 321.6 Conclusion and Future Prospects, 37References, 372 Ullmann Condensation Today: Arylation of Alcohols and Thiols with Aryl Halides 41Anis Tlili and Marc Taillefer2.1 Introduction, 412.2 Formation of C-O Bonds via Copper-Catalyzed Cross-Coupling Reactions with Aryl Halides, 422.3 Formation of C-S Bonds via Copper-Catalyzed Cross-Coupling Reactions with Aryl Halides, 672.4 Conclusion, 84References, 863 Copper-Catalyzed Formation of C-P Bonds with Aryl Halides 93Carole Alayrac and Annie-Claude Gaumont3.1 Introduction, 933.2 Arylation of Phosphines, 943.3 Arylation of Phosphine Oxides and Phosphites, 983.4 Conclusion, 110References, 1104 Alternative and Emerging Reagents for the Arylation of Heteronucleophiles 113Luc Neuville4.1 Introduction, 1134.2 Chan-Lam-Evans Coupling: Copper(II)-Promoted Oxidative Aryl Transfer from Arylboron Derivatives, 1154.3 Copper-Promoted Aryl Transfer from Metallated Aryl Derivatives (Nonboron), 1414.4 Copper-Catalyzed Arylation Reactions Involving Masked S- and N-Nucleophiles, 1514.5 Copper-Catalyzed Direct Heterofunctionalization of Aromatic C-H Bonds, 1604.6 Conclusion and Future Prospects, 178References, 1785 Beyond Ullmann-Goldberg Chemistry: Vinylation, Alkynylation, and Allenylation of Heteronucleophiles 187Kévin Jouvin and Gwilherm Evano5.1 Introduction, 1875.2 Copper-Mediated Alkenylation of Heteronucleophiles: Among the Best Routes to Heteroatom-Substituted Alkenes, 1895.3 Alkynylation of Heteronucleophiles: The Emergence of General Methods for the Synthesis of Heteroatom-Substituted Alkynes, 2195.4 Allenylation of Heteronucleophiles: New Tools for the Synthesis of Allenamides, 2325.5 Conclusion and Future Prospects, 233References, 2346 Aromatic/Vinylic Finkelstein Reaction 239Alicia Casitas and Xavi Ribas6.1 Introduction, 2396.2 Copper-Mediated Halogen Exchange Reactions in Aryl Halides, 2416.3 Most Recent Developments and Overview, 247References, 2497 Insights into the Mechanism of Modern Ullmann-Goldberg Coupling Reactions 253Alicia Casitas and Xavi Ribas7.1 General View and Key Mechanistic Aspects, 2537.2 Oxidation State of Copper Catalysts, 2547.3 Identity of the Active Copper(I) Complex, 2557.4 Activation Mode of Aryl Halides by Copper Complexes, 2617.5 Overview, Conclusions, and Future Prospects, 275References, 277PART II FORMATION OF C-C BONDS 2818 Modern Copper-Catalyzed Hurtley Reaction: Efficient C-Arylation of CH-Acid Derivatives 283Irina P. Beletskaya and Alexey Yu. Fedorov8.1 Introduction, 2838.2 Classical Hurtley Reaction, 2858.3 Ligation Effect in Copper-Catalyzed Reactions of Aryl Halides with Carbanions, 2868.4 Cascade Reactions Proceeding via a Hurtley Arylation Reaction, 2938.5 Mechanism of the Copper-Catalyzed C-Arylation Reactions, 3038.6 Concluding Remarks, 308References, 3089 Copper-Catalyzed Cyanations of Aryl Halides and Related Compounds 313Thomas Schareina and Matthias Beller9.1 Introduction, 3139.2 Modifications and Updates of Classical Cyanation Reactions (Rosenmund-von Braun, Sandmeyer), 3159.3 Copper-Catalyzed Cyanations of Aryl Halides, 3169.4 Copper-Mediated Oxidative Cyanations, 3249.5 Conclusion, 331References, 33110 Copper-Mediated Aryl-Aryl Bond Formation Leading to Biaryls: A Century after the Ullmann Breakthrough 335Yoshihiko Yamamoto10.1 Introduction, 33510.2 Biaryl Synthesis by Coupling of Aryl Halides and Diazonium Salts, 33610.3 Biaryl Synthesis by Coupling of Aryltin, Boron, and Silanes, 34710.4 Biaryl Synthesis by Arylation Involving Arene C-H or C-C Bond Fission, 35710.5 Biaryl Synthesis by Oxidative Coupling of 2-Naphthols, 37610.6 Conclusions and Outlook, 387References, 38811 Copper-Catalyzed Alkynylation, Alkenylation, and Allylation Reactions of Aryl Derivatives 401Ren-Jie Song and Jin-Heng Li11.1 Introduction, 40111.2 Copper-Catalyzed Alkynylation of Aryl Derivatives, 40211.3 Copper-Catalyzed Alkenylation of Aryl Derivatives, 43211.4 Copper-Catalyzed Strategies for the Formation of Allyl-Aryl Bonds, 44511.5 Conclusion and Outlook, 450References, 45012 Copper-Catalyzed Alkynylation and Alkenylation Reactions of Alkynyl Derivatives: New Access to Diynes and Enynes 455Ruimao Hua12.1 Introduction, 45512.2 Copper-Catalyzed Synthesis of Symmetrical and Unsymmetrical 1,3-Diynes, 45612.3 Copper-Catalyzed Synthesis of 1,4-Diynes, 46812.4 Synthesis of 1,3-Enynes by Direct Reaction of Vinyl Halides with Alkynes, 46812.5 Synthesis of 1,3-Enynes by Stille-Type Cross-Coupling Reaction, 47412.6 Synthesis of 1,3-Enynes by the Suzuki-Miyaura-Type Cross-Coupling Reaction, 47612.7 Synthesis of 1,4-Enynes by Allylation Reaction of Terminal Alkynes, 47812.8 Conclusion, 480References, 48013 Copper-Mediated Alkenylation Reaction of Alkenyl Derivatives: A Straightforward Elaboration of 1,3-Dienes 485Hao Li, Songbai Liu, and Lanny S. Liebeskind13.1 Introduction, 48513.2 Symmetrical 1,3-Dienes by Homocoupling Reaction of Vinyl Derivatives, 48613.3 Unsymmetrical 1,3-Dienes by Cross-Coupling Reactions, 49613.4 Conclusions, 510References, 51114 Emerging Areas in Copper-Mediated Trifl uoromethylations of Aryl Derivatives: Catalytic and Oxidative Cross-Coupling Processes 515Kévin Jouvin, Céline Guissart, Cédric Theunissen, and Gwilherm Evano14.1 Introduction, 51514.2 Copper-Catalyzed Trifluoromethylation of Aryl Halides: A Long-Lasting Quest Finally Reached, 51714.3 Copper-Mediated Oxidative Trifl uoromethylation Reactions, 52314.4 Conclusion and Future Prospects, 528References, 528PART III APPLICATIONS OF COPPER-CATALYZED CROSS-COUPLING REACTIONS: HETEROCYCLES, NATURAL PRODUCTS, PROCESS, AND SUSTAINABLE CHEMISTRY 53115 Copper-Mediated Cyclization Reactions: New Entries to Heterocycles 533Daoshan Yang and Hua Fu15.1 Introduction, 53315.2 Cyclization by C-N Bond Formation, 53415.3 Cyclization by C-O Bond Formation, 56015.4 Cyclization by C-C Bond Formation, 56715.5 Copper-Catalyzed Double Cross-Coupling Reactions for the Assembly of Heterocycles, 57615.6 Conclusion and Future Prospects, 583References, 58416 Application of Copper-Mediated C-N Bond Formation in Complex Molecules Synthesis 589Jihoon Lee and James S. Panek16.1 Introduction, 58916.2 Aryl Amination in Complex Molecule Synthesis, 59016.3 Aryl Amidation in Complex Molecule Synthesis, 59516.4 Arylation of N-Heterocycles in Complex Molecule Synthesis, 60116.5 Vinyl Amidation in Complex Molecule Synthesis, 60616.6 Alkyne Amidation in Complex Molecule Synthesis, 62016.7 Intramolecular C-N Bond Formation in Natural Product Synthesis, 62216.8 Summary and Outlook, 637References, 63817 Natural Products and C-O/C-S Bond-Forming Reactions: Copper Showed the Way 643Doron Pappo17.1 Introduction, 64317.2 Total Synthesis of Naturally Occurring Diaryl Ethers by Arylation of Phenols, 64417.3 Intramolecular Diaryl Ether Bond-Forming Reactions, 65917.4 Arylation of Alcohols, 66617.5 Vinylation of Alcohols, 67317.6 Copper-Mediated C-S Bond Formation in Natural Product Synthesis, 67517.7 Conclusion and Future Prospects, 677References, 67818 Copper-Catalyzed C-C Bond Formation in Natural Product Synthesis: Elegant and Efficient Solutions to a Key Bond Disconnection 683Morgan Donnard and Nicolas Blanchard18.1 Introduction, 68318.2 Natural Biaryls by Copper-Catalyzed Cross Coupling, 68418.3 Copper-Catalyzed 1,3-Enyne Formation, 69118.4 Copper-Mediated Synthesis of Dienes, Trienes, and Extended Polyenes, 69418.5 Copper-Catalyzed Synthesis of 1,N-Polyynes Natural Products, 71118.6 Conclusions and Future Prospects, 718References, 71919 Process Chemistry and Copper Catalysis 725Klaus Kunz and Norbert Lui19.1 Introduction and Scope, 72519.2 Copper versus Palladium, 72719.3 Applications, 72719.4 Conclusion, 739References, 74020 Reusable Catalysts for Copper-Mediated Cross-Coupling Reactions under Heterogeneous Conditions 745Zhiyong Wang, Changfeng Wan, and Ye Wang20.1 Introduction, 74520.2 Copper Nanoparticle-Catalyzed Cross-Coupling Reactions, 74620.3 Supported Copper-Catalyzed Cross-Coupling Reaction, 76620.4 Conclusion, 780References, 780INDEX 785