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 explores the most recent progress and new developments 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 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 contains the most recent information available on the developments and applications in the field of catalytic cyclization reactions using rhodium complexes.

Ken Tanaka is a Professor of Applied Chemistry in the Department of Chemical Science and Engineering at the Tokyo Institute of Technology. Since the start of his academic career in 2003, he has published over 190 scientific papers and one book. His research focuses on organometallic chemistry directed toward organic synthesis.

Inhalt

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

1.2.1 P-Chirogenic Bisphosphine Ligands 4

1.2.1.1 Electron-Rich C2 Symmetric Ligands 4

1.2.1.2 Three-Hindered Quadrant Ligands 5

1.2.1.3 Ligands Bearing Two or Three Aryl Groups at the Phosphorus Atom 5

1.2.2 DuPhos, BPE, and Analogous Ligands 6

1.2.3 Ferrocene-Based Bisphosphine Ligands 7

1.2.4 C2 Symmetric Triaryl- or Diarylphosphine Ligands with Axial Chirality 9

1.2.5 PhosphinePhosphite and PhosphinePhosphoramide Ligands 9

1.2.6 Other Bidentate Ligands 9

1.2.7 Monodentate Phosphorus Ligands 11

1.3 Application of Chiral Phosphorus Ligands in Rhodium-Catalyzed Asymmetric Hydrogenation 12

1.3.1 Hydrogenation of Alkenes 12

1.3.1.1 Hydrogenation of Enamides 12

1.3.1.2 Hydrogenation of Enol Esters 18

1.3.1.3 Hydrogenation of ,-Unsaturated Acids, Esters, and Related Substrates 19

1.3.1.4 Hydrogenation of Other Functionalized Alkenes 21

1.3.1.5 Hydrogenation of Unfunctionalized Alkenes 24

1.3.1.6 Hydrogenation of Heteroarenes 24

1.3.2 Hydrogenation of Ketones 25

1.3.3 Hydrogenation of Imines, Oximes, and Hydrazones 26

1.4 EnantioselectionMechanism of Rhodium-Catalyzed Asymmetric Hydrogenation 27

1.5 Conclusion 28

References 29

2 Rhodium(I)-Catalyzed Hydroboration and Diboration 39
Kohei Endo

2.1 Introduction 39

2.2 Hydroboration of Alkenes 39

2.2.1 Development of Catalyst Systems 39

2.2.2 Enantioselective Reactions 41

2.2.3 Hydroboration of FunctionalizedMolecules 44

2.3 Diboration 45

2.3.1 1,1-Diboration Reactions 45

2.3.2 1,2-Diboration Reactions 45

2.4 Conclusion 46

References 47

3 Rhodium(I)-Catalyzed Hydroformylation and Hydroamination 49
Zhiwei Chen and VyM. Dong

3.1 Introduction 49

3.2 Rhodium(I)-Catalyzed Hydroformylation 49

3.2.1 Asymmetric Hydroformylation of Challenging Substrates 49

3.2.2 Transfer Hydroformylation 50

3.3 Rhodium(I)-Catalyzed Hydroamination 54

3.3.1 Asymmetric Rhodium(I)-Catalyzed Hydroamination 54

3.3.2 Anti-Markovnikov Rhodium(I)-Catalyzed Hydroamination 56

3.4 Conclusion 59

References 61

4 Rhodium(I)-Catalyzed Hydroacylation 63
Maitane Fernández andMichael C.Willis

4.1 Introduction 63

4.2 Rhodium(I)-Catalyzed Intramolecular Hydroacylation 63

4.2.1 Small Ring Synthesis: Five-Membered Rings 63

4.2.2 Larger Ring Synthesis: Six-, Seven-, and Eight-Membered Rings 66

4.3 Rhodium(I)-Catalyzed Intermolecular Hydroacylation 68

4.3.1 N-Based Chelation Control 69

4.3.2 O-Based Chelation Control 70

4.3.3 S-Based Chelation Control 73

4.3.4 C=O as a Directing Group for Hydroacylation 79

4.4 Conclusion 81

References 81

5 Rhodium(I)-Catalyzed Asymmetric Addition of Organometallic Reagents to Unsaturated Compounds 85
Hsyueh-LiangWu and Ping-YuWu

5.1 Introduction 85

5.2 ,-Unsaturated Ketones 85

5.2.1 Chiral Phosphorus Ligands 85

5.2.2 Chiral Diene Ligands 89

5.2.3 Chiral Bis-sulfoxide Ligands 92

5.2.4 Chiral Hybrid Ligands 92

5.3 ,-Unsaturated Aldehydes 95

5.4 ,-Unsaturated Esters 98

5.5 ,-Unsaturated Amides 102

5.6 ,-Unsaturated Phosphonates 105

5.7 ,-Unsaturated Sulfonyl Compounds 105

5.8 Nitroolefin Compounds 107

5.9 Alkenylheteroarene and Alkenylarene Compounds 11...