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 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.

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 CHETEROATOM BONDS 1

1 Modern UllmannGoldberg 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 CO Bonds via Copper-Catalyzed Cross-Coupling Reactions with Aryl Halides, 42

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

2.4 Conclusion, 84

References, 86

3 Copper-Catalyzed Formation of CP 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 ChanLamEvans 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 CH Bonds, 160

4.6 Conclusion and Future Prospects, 178

References, 178

5 Beyond UllmannGoldberg 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 UllmannGoldberg 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 CC 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...