Copper-Mediated Cross-Coupling Reactions

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.

• 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 Trifluoromethylations 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 Trifluoromethylation 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

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