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An essential reference to the highly effective reactions applied to modern organic synthesis
Rhodium complexes are one of the most important transition metals for organic synthesis due to their ability to catalyze a variety of useful transformations. Rhodium Catalysis in Organic Synthesis: Methods and Reactions explores the most recent progress and new developments particularly in the field of catalytic cyclization reactions using rhodium(I) complexes and catalytic carbon-hydrogen bond activation reactions using rhodium(II) and rhodium(III) complexes.
Edited by a noted expert in the field with contributions from a panel of leading international scientists, Rhodium Catalysis in Organic Synthesis: Methods and Reactions presents the essential information in one comprehensive volume. Designed to be an accessible resource, the book is arranged by different reaction types. All the chapters provide insight into each transformation and include information on the history, selectivity, scope, mechanism, and application. In addition, the chapters offer a summary and outlook of each transformation. This important resource:
- Offers a comprehensive review of how rhodium complexes catalyze a variety of highly useful reactions for organic synthesis (e.g. coupling reactions, CH-bond functionalization, hydroformylation, cyclization reactions and others)
- Includes information on the most recent developments that contain a range of new, efficient, elegant, reliable and useful reactions
- Presents a volume edited by one of the international leading scientists working in the field today
- Contains the information that can be applied by researchers in academia and also professionals in pharmaceutical, agrochemical and fine chemical companies
Written for academics and synthetic chemists working with organometallics, Rhodium Catalysis in Organic Synthesis: Methods and Reactions contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.
Table of Contents
Preface xv
Part I Rhodium(I) Catalysis 1
1 Rhodium(I)-Catalyzed Asymmetric Hydrogenation 3
Tsuneo Imamoto
1.1 Introduction 3
1.2 Chiral Phosphorus Ligands 3
1.3 Application of Chiral Phosphorus Ligands in Rhodium-Catalyzed Asymmetric Hydrogenation 12
1.4 Enantioselection Mechanism of Rhodium-Catalyzed Asymmetric Hydrogenation 27
1.5 Conclusion 28
2 Rhodium(I)-Catalyzed Hydroboration and Diboration 39
Kohei Endo
2.1 Introduction 39
2.2 Hydroboration of Alkenes 39
2.3 Diboration 45
2.4 Conclusion 46
3 Rhodium(I)-Catalyzed Hydroformylation and Hydroamination 49
Zhiwei Chen and VyM. Dong
3.1 Introduction 49
3.2 Rhodium(I)-Catalyzed Hydroformylation 49
3.3 Rhodium(I)-Catalyzed Hydroamination 54
3.4 Conclusion 59
4 Rhodium(I)-Catalyzed Hydroacylation 63
Maitane Fernández and Michael C. Willis
4.1 Introduction 63
4.2 Rhodium(I)-Catalyzed Intramolecular Hydroacylation 63
4.3 Rhodium(I)-Catalyzed Intermolecular Hydroacylation 68
4.4 Conclusion 81
5 Rhodium(I)-Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds 85
Hsyueh-Liang Wu and Ping-Yu Wu
5.1 Introduction 85
5.2 α,β-Unsaturated Ketones 85
5.3 α,β-Unsaturated Aldehydes 95
5.4 α,β-Unsaturated Esters 98
5.5 α,β-Unsaturated Amides 102
5.6 α,β-Unsaturated Phosphonates 105
5.7 α,β-Unsaturated Sulfonyl Compounds 105
5.8 Nitroolefin Compounds 107
5.9 Alkenylheteroarene and Alkenylarene Compounds 111
5.10 Conclusion 111
6 Rhodium(I)-Catalyzed Allylation with Alkynes and Allenes 117
Adrian B. Pritzius and Bernhard Breit
6.1 Introduction 117
6.2 Rh(I)-Catalyzed Addition of O-Nucleophiles 117
6.3 Rh(I)-Catalyzed Addition of S-Nucleophiles 123
6.4 Rh(I)-Catalyzed Addition of N-Nucleophiles 124
6.5 Rh(I)-Catalyzed Addition of C-Nucleophiles 127
6.6 Application of Rhodium-Catalyzed Addition in Total Synthesis 127
6.7 Conclusion 129
7 Rhodium(I)-Catalyzed Reductive Carbon–Carbon Bond Formation 133
Adam D. J. Calow and John F. Bower
7.1 Introduction 133
7.2 Hydroformylation 133
7.3 Reductive C—C Bond Formation Between Electron-Deficient Alkenes and Carbonyls or Imines 137
7.4 Reductive C—C Bond Formation Between Less Polarized Carbon-Based π-Unsaturated Systems and Carbonyls, Imines, or Anhydrides 144
7.5 Reductive C—C Bond Formation Between Carbon-Based π-Unsaturated Systems 151
7.6 Conclusions 156
8 Rhodium(I)-Catalyzed [2+2+1] and [4+1] Cycloadditions 161
Tsumoru Morimoto
8.1 Introduction 161
8.2 [2+2+1] Cycloaddition 161
8.3 [4+1] Cycloaddition 176
8.4 Conclusion 179
9 Rhodium(I)-Catalyzed [2+2+2] and [4+2] Cycloadditions 183
Yu Shibata and Ken Tanaka
9.1 Introduction 183
9.2 [2+2+2] Cycloaddition 183
9.3 [4+2] Cycloaddition 214
9.4 Conclusion 222
10 Rhodium(I)-Catalyzed Cycloadditions Involving Vinylcyclopropanes and Their Derivatives 229
Xing Fan, Cheng-Hang Liu, and Zhi-Xiang Yu
10.1 Introduction 229
10.2 VCP Isomerization Catalyzed by Rh(I) 230
10.3 Cycloaddition Reactions Using VCPs 5C Synthon 231
10.4 Cycloaddition Reactions Using VCPs 3C Synthon 255
10.5 Miscellaneous Cycloaddition 266
10.6 Conclusion 270
11 Rhodium(I)-Catalyzed Reactions via Carbon–Hydrogen Bond Cleavage 277
Takanori Shibata
11.1 Introduction 277
11.2 C–H Arylation 277
11.3 C–H Alkylation 279
11.4 C–H Alkenylation 283
11.5 Tandem Reaction Initiated by C–H Activation 285
11.6 C–H Borylation 287
11.7 Undirected Dehydrogenative C–H/Si–H Coupling 290
11.8 Conclusion 295
12 Rhodium(I)-Catalyzed Reactions via Carbon–Carbon Bond Cleavage 299
Masahiro Murakami and Naoki Ishida
12.1 Introduction 299
12.2 Reactions of Cyclopropanes and Cyclobutanes 299
12.3 Reactions via Cleavage of C(Carbonyl)—C Bonds 310
12.4 Reactions via Directing Group-Assisted C—C Bond Cleavage 315
12.5 Reactions of Alcohols via C—C Bond Cleavage 323
12.6 Reactions via Cleavage of C—CN Bond 330
12.7 Reactions via Decarbonylation of Aldehydes and Carboxylic Acid Derivatives 332
12.8 Conclusion 333
Part II Rhodium(II) Catalysis 341
13 Rhodium(II) Tetracarboxylate-Catalyzed Enantioselective C–H Functionalization Reactions 343
Sidney M. Wilkerson-Hill and Huw M. L. Davies
13.1 Introduction 343
13.2 Mechanistic Insights and General Considerations 344
13.3 Development of Rh2(S-DOSP)4 as a Chiral Catalyst for C–H Functionalization 347
13.4 Combined C–H Functionalization/Cope Rearrangement 350
13.5 Phthalimido Amino Acid-Derived Catalysts for Intramolecular C–H Functionalization 353
13.6 Development of Triarylcyclopropane Carboxylate Rh(II) Complexes for Catalyst-Controlled Site-Selective C–H Functionalization 359
13.7 Emerging Chiral Dirhodium Catalyst for Enantioselective C–H Functionalization 364
13.8 New Paradigms in the Logic of Chemical Synthesis 365
13.9 Conclusion 368
14 Rhodium(II)-Catalyzed Nitrogen-Atom Transfer for Oxidation of Aliphatic C—H Bonds 373
TomG. Driver
14.1 Introduction 373
14.2 Mechanism-Inspired Development of New Rh2(II) Catalysts 374
14.3 The Development of New Intramolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 383
14.4 Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination Using an Iodine(III) Oxidant to Generate the Nitrene 400
14.5 Non-Oxidatively Generated Nitrenes in Intermolecular Rh2(II)-Catalyzed sp3-C—H Bond Amination 411
14.6 Diastereoselective Rh2(II)-Catalyzed sp3-C—H Bond Amination Using Chiral, Non-racemic Nitrogen-Atom Precursors 416
14.7 Enantioselective Rh2(II)-Catalyzed sp3-C—H Bond Amination 422
14.8 Conclusion 429
15 Rhodium(II)-Catalyzed Cyclopropanation 433
Vincent N.G. Lindsay
15.1 Introduction 433
15.2 Intermolecular Cyclopropanation of Alkenes 436
15.3 Intramolecular Cyclopropanation of Alkenes 443
15.4 Cyclopropanation of Poorly Nucleophilic π-Systems: Alkynes, Arenes, and Allenes as Substrates 444
15.5 Conclusion 445
16 Reactions of α-Imino Rhodium(II) Carbene Complexes Generated from N-Sulfonyl-1,2,3-Triazoles 449
Tomoya Miura and Masahiro Murakami
16.1 Introduction 449
16.2 Synthesis of N-Sulfonyl-1,2,3-Triazoles 451
16.3 Reactions of Carbon Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 451
16.4 Reactions of Oxygen and Sulfur Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 458
16.5 Reactions of Nitrogen Nucleophiles with α-Imino Rhodium(II) Carbene Complexes 464
16.6 Conclusion 466
17 Rhodium(II)-Catalyzed 1,3- and 1,5-Dipolar Cycloaddition 471
Nirupam De, Donguk Ko, and Eun Jeong Yoo
17.1 Introduction 471
17.2 1,3-Dipolar Cycloadditions of Carbonyl Ylides 471
17.3 1,3-Dipolar Cycloadditions of Azomethine Ylides 478
17.4 1,3-Dipolar Cycloadditions of Enoldiazo Compounds 479
17.5 1,5-Dipolar Cycloadditions of Pyridinium Zwitterions 482
17.6 Conclusion 484
Part III Rhodium(III) Catalysis 487
18 Rhodium(III)-Catalyzed Annulative Carbon–Hydrogen Bond Functionalization 489
Tetsuya Satoh and Masahiro Miura
18.1 Introduction 489
18.2 Type A Annulation 490
18.3 Type B Annulation 508
18.4 Type C Annulation 510
18.5 Type D Cyclization 515
18.6 Conclusion 516
19 Rhodium(III)-Catalyzed Non-annulative Carbon–Hydrogen Bond Functionalization 521
Fang Xie and Xingwei Li
19.1 Introduction 521
19.2 Alkenylation and Arylation 522
19.3 Alkynylation 540
19.4 Alkylation 541
19.5 C—N Bond Formation 564
19.6 Introduction of C=O Bond 577
19.7 Cyanation 579
19.8 C—O Bond Formation 580
19.9 C—X Bond Formation 581
19.10 Non-annulative Thiolation of Arenes 585
19.11 C—Se Bond Formation 585
19.12 Conclusion 586
20 Sterically and Electronically Tuned Cp Ligands for Rhodium(III)-Catalyzed Carbon–Hydrogen Bond Functionalization 593
Fedor Romanov-Michailidis, Erik J.T. Phipps, and Tomislav Rovis
20.1 Introduction 593
20.2 Quantitative Models for Steric and Electronic Parameterization of Cp Ligands on Rhodium(III) 594
20.3 Sterically Tuned Cp Ligands 598
20.4 Electronically Tuned Cp Ligands 612
20.5 Conclusion 626
21 Chiral Cp Ligands for Rhodium(III)-Catalyzed Asymmetric Carbon–Hydrogen Bond Functionalization 629
Christopher G. Newton and Nicolai Cramer
21.1 Introduction 629
21.2 Seminal Work 629
21.3 The Ligands 630
21.4 Applications 634
21.5 Conclusion 642
References 642
Index 645
