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
