Ligand Platforms in Homogenous Catalytic Reactions with Metals

Serving as a user's manual for synthetic organic and catalytic chemists, this book guides chemists in the design and choice of ligands to catalyze organic reactions and apply the results for more efficient, green, and practical synthesis.

• Focuses on the role of ligands in metal complexes that catalyze green organic transformations: a hot topic in the area of organic synthesis and green chemistry
• Offers a comprehensive resource to help readers design and choose ligands and understand selectivity/reactivity characteristics
• Addresses a gap by taking novel ligand approaches and including up-to-date discussion on hydrogen transfers and reactions
• Presents important industrial perspective and provides rational explanations of ligand effects, impacts, and novelty

Preface ix

Abbreviation xi

Part I N-Heterocyclic Carbene Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 1

1 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 3

1.1 Introduction, 3

1.2 Oxidation of Alcohols Based on Hydrogen Transfer, 3

1.3 Oxidation of Alcohols Based on Dehydrogenation, 10

1.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 12

1.5 Other Related Hydrogenative Reactions, 21

References, 25

2 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing N-Heterocyclic Carbene Ligands 27

2.1 Introduction, 27

2.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 27

2.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 37

2.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 46

References, 52

Part ii η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 55

3 Oxidation and Hydrogenation Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 57

3.1 Introduction, 57

3.2 Oxidation of Alcohol Based on Hydrogen Transfer and Dehydrogenation, 59

3.3 Oxidation of Amine Based on Hydrogen Transfer, 68

3.4 Hydrogenation and Transfer Hydrogenation of Carbonyl Compounds, 71

3.5 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 79

References, 84

4 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing η4-Cyclopentadienone/η5-Hydroxycyclopentadienyl and Related Ligands 87

4.1 Introduction, 87

4.2 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 88

4.3 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 97

4.4 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer and Dehydrogenation, 102

References, 105

Part iii Pincer Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 107

5 Dehydrogenation of Alkanes Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 109

5.1 Introduction, 109

5.2 Conversion of Alkanes into Alkenes Based on Hydrogen Transfer, 109

5.3 Dehydroaromatization of Alkanes Based on Hydrogen Transfer, 115

5.4 Alkane Metathesis by Tandem Alkane Dehydrogenation and Alkene Metathesis, 118

5.5 Conversion of Alkanes into Alkenes Based on Dehydrogenation, 121

References, 126

6 Oxidation and Hydrogenation Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 128

6.1 Introduction, 128

6.2 Oxidation of Alcohols Based on Hydrogen Transfer and Dehydrogenation, 128

6.3 Dehydrogenation of Amines, 137

6.4 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds, 141

References, 157

7 Bond-Forming Reactions Catalyzed by Transition Metal Complexes Bearing Pincer Ligands 159

7.1 Introduction, 159

7.2 Carbon–Carbon Bond Formation Based on Hydrogen Transfer, 159

7.3 Carbon–Nitrogen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 161

7.4 Carbon–Oxygen Bond Formation Based on Hydrogen Transfer and Dehydrogenation, 173

References, 182

Part iv Bidentate and Miscellaneous Ligands in Transition Metal Catalyzed Hydrogen Transfer and Dehydrogenative Reactions 183

8 Oxidation and Dehydrogenation of Alcohols and Amines Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 185

8.1 Introduction, 185

8.2 Oxidation of Alcohols Based on Hydrogen Transfer with Oxidant, 185

8.3 Dehydrogenative Oxidation of Alcohols without Oxidant, 209

8.4 Oxidation of Amines Based on Hydrogen Transfer and Dehydrogenation, 220

References, 224

9 Hydrogenation and Transfer Hydrogenation of Carbon–Heteroatom Unsaturated Bonds Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 228

9.1 Introduction, 228

9.2 Hydrogenation and Transfer Hydrogenation of Carbonyl and Related Compounds, 229

9.3 Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds, 263

References, 274

10 Bond-Forming Reactions Based on Hydrogen Transfer Catalyzed by Well-Defined Transition Metal Complexes Bearing Bidentate and Miscellaneous Ligands 278

10.1 Introduction, 278

10.2 Carbon–Carbon Bond-Forming Reactions Based on Hydrogen Transfer, 279

10.3 Carbon–Nitrogen Bond-Forming Reactions Based on Hydrogen Transfer, 296

10.4 Carbon–Oxygen Bond-Forming Reactions Based on Hydrogen Transfer, 321

References, 330

Index 335

Ryohei Yamaguchi is an Emeritus Professor of Chemistry at Kyoto University, Japan. Previously, he worked as a postdoctoral fellow at University of Minnesota. His research includes the development of selective and catalytic organic reactions by means of metal reagents/complexes directed towards green organic synthesis.

Ken-ichi Fujita is an Associate Professor of Chemistry at Kyoto University, Japan. Previously, he worked as a postdoctoral fellow at Yale University, USA and received the Incentive Award in Synthetic Organic Chemistry, Japan in 2006. His research focuses on the development of new catalytic systems for green organic synthesis.

The selection of ligands is critical to carrying out practical and efficient reactions, and there has been an increasing desire to devise and develop greener alternatives for such chemical transformations. Chemists must consider the importance of ligands in transition metal complexes used as catalysts-- including selectivity and reactivity characteristics and how to choose different ligands in order to perform practical and efficient synthesis.

Motivated by such a pressing need, this book serves as a manual for synthetic organic and catalytic chemists – guiding them in the design and choice of ligands to catalyze green organic transformations. Offering a useful resource, the authors present important industrial perspective and provide rational explanations of ligand effects, impacts, and novelty. Divided into four parts, the book covers different ligands and reactions: N-heterocyclic carbene ligands, cyclopentadienone and related functional ligands, pincer ligands, and notable miscellaneous ligands; all in transition metal catalyzed hydrogen transfer and dehydrogenative reactions. Additional features include:

• Discussion of ligand selectivity/reactivity characteristics

• Up-to-date discussion on hydrogen transfers and related reactions

• Emphasis on ligand designs and applications necessary for more practical and efficient syntheses


While scattered literature on efficient ligands for transformations exists on the topics, this book compiles the most up-to-date and necessary information emphasizing design and application under one cover