Gwilherm Evano, Nicolas Blanchard

Copper-Mediated Cross-Coupling Reactions (eBook, PDF)

• Format: PDF

Produktbeschreibung

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.

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Produktdetails

• Verlag: Jossey-Bass
• Erscheinungstermin: 23. September 2013
• Englisch
• ISBN-13: 9781118690680
• Artikelnr.: 39567306

Autorenporträt

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.

Inhaltsangabe

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 Trifluoromethylations 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 Trifluoromethylation 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