Wiley
Wiley.com
Print this page Share

Metal-Catalyzed Reactions in Water

Pierre Dixneuf (Editor), Victorio Cadierno (Editor)
ISBN: 978-3-527-33188-8
426 pages
February 2013
Metal-Catalyzed Reactions in Water (3527331883) cover image
Water is abundant in nature, non-toxic, non-flammable and renewable and could therefore be safer and economical for the chemical industry
wherever it is used as a solvent. This book provides a comprehensive overview of developments in the use of water as a solvent for metal
catalysis, illustrating the enormous potential of water in developing new catalytic transformations for fi ne chemicals and molecular materials
synthesis. A group of international experts cover the most important metalcatalyzed reactions in water and bring together cutting-edge results
from recent literature with the first-hand knowledge gained by the chapter authors. This is a must-have book for scientists in academia
and industry involved in the fi eld of catalysis, greener organic synthetic methods, water soluble ligands and catalyst design, as well as for teachers and students interested in innovative and sustainable chemistry.
See More

Preface XIII

List of Contributors XV

1 Metal-Catalyzed Cross-Couplings of Aryl Halides to Form C–C Bonds in Aqueous Media 1
Kevin H. Shaughnessy

1.1 Introduction 1

1.2 Aqueous-Phase Cross-Coupling Using Hydrophilic Catalysts 3

1.2.1 Hydrophilic Triarylphosphines and Diarylalkylphospines 3

1.2.2 Sterically Demanding, Hydrophilic Trialkyl and Dialkylbiarylphosphines 7

1.2.3 NHC Ligands 10

1.2.4 Nitrogen Ligands 13

1.2.5 Palladacyclic Complexes 15

1.3 Cross-Coupling in Aqueous Media Using Hydrophobic Ligands 17

1.3.1 Surfactant-Free Reactions 17

1.3.2 Surfactant-Promoted Reactions 20

1.3.2.1 Cationic Surfactants 21

1.3.2.2 Anionic Surfactants 22

1.3.2.3 Nonionic Surfactants 22

1.4 Heterogeneous Catalysts in Aqueous Media 25

1.4.1 Supported Palladium–Ligand Complexes 25

1.4.1.1 Polymer-Supported Palladium Complexes 25

1.4.1.2 Palladium Complexes Supported on Inorganic Materials 27

1.4.2 Nanoparticle-Catalyzed Coupling 29

1.4.2.1 Unsupported Palladium Nanoparticle Catalysts 29

1.4.2.2 Polymer-Supported Nanoparticles 30

1.4.2.3 Inorganic-Supported Nanoparticle Catalysts 33

1.5 Special Reaction Conditions 35

1.5.1 Microwave Heating 35

1.5.2 Ultrasound 36

1.5.3 Thermomorphic Reaction Control 36

1.6 Homogeneous Aqueous-Phase Modification of Biomolecules 37

1.6.1 Amino Acids and Proteins 37

1.6.2 Nucleosides and Nucleotides 38

1.7 Conclusion 39

References 39

2 Metal-Catalyzed C–H Bond Activation and C–C Bond Formation in Water 47
Bin Li and Pierre H. Dixneuf

2.1 Introduction 47

2.2 Catalytic Formation of C–C Bonds from spC–H Bonds in Water 48

2.2.1 Catalytic Nucleophilic Additions of Alkynes in Water 48

2.2.2 Addition of Terminal Alkynes to C≡C Bonds in Water 49

2.2.3 The Sonogashira-Type Reactions in Water 49

2.3 Activation of sp2C–H Bonds for Catalytic C–C Bond Formation in Water 53

2.3.1 Homocoupling of sp2C–H Bonds 53

2.3.2 Direct C–H Bond Arylation of Alkenes and Aryl Boronic Acid Derivatives 55

2.3.3 Cross-Coupling Reactions of sp2C–H Bonds with sp2C-X Bonds in Water 56

2.3.3.1 Direct C–H Bond Arylations with Aryl Halides and Palladium Catalysts 56

2.3.3.2 Direct C–H Bond Arylations with Aryl Halides and Ruthenium Catalysts 62

2.3.4 Cross-Coupling Reactions of sp2C–H Bonds with Carbon Nucleophiles in Water 64

2.3.5 Oxidative Cross-Coupling of sp2C–H Bond Reactions in Water 65

2.3.5.1 Alkenylations of Arenes and Heteroarenes with Palladium Catalysts 65

2.3.5.2 Alkenylation of Heterocycles Using In(OTf)3 Catalyst 68

2.3.5.3 Alkenylation of Arenes and Heteroarenes with Ruthenium(II) Catalysts 69

2.4 Activation of sp3C–H Bonds for Catalytic C–C Bond Formation in Water 73

2.4.1 Selective sp3C–H Activation of Ketones 73

2.4.2 Catalytic Enantioselective Alkynylation of sp3C–H Bonds 74

2.4.3 Cross-Dehydrogenative Coupling between sp3C–H Bonds Adjacent to a Heteroatom 75

2.4.4 Catalytic Enolate Carbon Coupling with (Arene) C–X Carbon 77

2.4.5 Arylation of sp3C–H Bonds with Aryl Halides or sp2C–H Bond 79

2.5 Conclusion 80

Acknowledgments 81

References 81

3 Catalytic Nucleophilic Additions of Alkynes in Water 87
Xiaoquan Yao and Chao-Jun Li

3.1 Introduction 87

3.2 Catalytic Nucleophilic Additions of Terminal Alkynes with Carbonyl Derivatives 88

3.2.1 Reaction with Acid Chlorides 89

3.2.2 Reaction with Aldehydes 89

3.2.3 Reaction with Ketones 95

3.3 Addition of Terminal Alkyne to Imine, Tosylimine, Iminium Ion, and Acyl Iminium Ion 96

3.3.1 Reaction with Imines 97

3.3.2 Reaction with Iminium Ions 99

3.3.3 Reaction with Acylimine and Acyliminium Ions 102

3.4 Direct Conjugate Addition of Terminal Alkynes 103

3.5 Conclusions 105

Acknowledgments 105

References 106

4 Water-Soluble Hydroformylation Catalysis 109
Duc Hanh Nguyen, Martine Urrutigo¨•ty, and Philippe Kalck

4.1 Introduction 109

4.2 Hydroformylation of Light C2–C5 Alkenes in the RCH/RP Process 110

4.3 Hydroformylation of Alkenes Heavier than C5 115

4.3.1 Water-Soluble and Amphiphilic Ligands 116

4.3.2 Phase-Transfer Agents: Cyclodextrins and Calixarenes 120

4.3.3 Supported Aqueous-Phase Catalysis 125

4.4 Innovative Expansions 128

4.4.1 Thermoregulated Catalytic Systems 128

4.4.2 Ionic Liquids and Carbon Dioxide Induced Phase Switching 129

4.4.3 Cascade Reactions 130

4.5 Conclusion 132

References 133

5 Green Catalytic Oxidations in Water 139
Roger A. Sheldon

5.1 Introduction 139

5.2 Examples of Water-Soluble Ligands 140

5.3 Enzymatic Oxidations 140

5.4 Biomimetic Oxidations 142

5.5 Epoxidation, Dihydroxylation, and Oxidative Cleavage of Olefins 143

5.5.1 Tungsten-Based Systems 144

5.5.2 Manganese- and Iron-Based Systems 145

5.5.3 Ruthenium and Platinum Catalysts 148

5.5.4 Other Systems 149

5.6 Alcohol Oxidations 151

5.6.1 Tungsten (VI) Catalysts 151

5.6.2 Palladium Diamine Complexes as Catalysts 153

5.6.3 Noble Metal Nanoparticles as Quasi-Homogeneous Catalysts 156

5.6.4 Ruthenium and Manganese Catalysts 158

5.6.5 Organocatalysts: Stable N-Oxy Radicals and Hypervalent Iodine Compounds 158

5.6.6 Enzymatic Oxidation of Alcohols 161

5.7 Sulfoxidations in Water 161

5.7.1 Tungsten- and Vanadium-Catalyzed Oxidations 162

5.7.2 Enantioselective Sulfoxidation with Enzymes 163

5.7.3 Flavins as Organocatalysts for Sulfoxidation 165

5.8 Conclusions and Future Outlook 166

References 166

6 Hydrogenation and Transfer Hydrogenation in Water 173
Xiaofeng Wu and Jianliang Xiao

6.1 Introduction 173

6.2 Water-Soluble Ligands 174

6.2.1 Water-Soluble Achiral Ligands 175

6.2.2 Water-Soluble Chiral Ligands 175

6.3 Hydrogenation in Water 176

6.3.1 Achiral Hydrogenation 176

6.3.1.1 Hydrogenation of Olefins 176

6.3.1.2 Hydrogenation of Carbonyl Compounds 183

6.3.1.3 Hydrogenation of Aromatic Rings 185

6.3.1.4 Hydrogenation of Other Organic Groups 187

6.3.1.5 Hydrogenation of CO2 188

6.3.2 Asymmetric Hydrogenation 191

6.3.2.1 Asymmetric Hydrogenation of Olefins 191

6.3.2.2 Asymmetric Hydrogenation of Carbonyl and Related Compounds 194

6.3.2.3 Asymmetric Hydrogenation of Imines 196

6.4 Transfer Hydrogenation in Water 197

6.4.1 Achiral Transfer Hydrogenation 198

6.4.1.1 Achiral Transfer Hydrogenation of Carbonyl Compounds 198

6.4.1.2 Achiral Transfer Hydrogenation of Imino Compounds 203

6.4.2 Asymmetric Transfer Hydrogenation 204

6.4.2.1 Asymmetric Transfer Hydrogenation of C=C Double Bonds 204

6.4.2.2 Asymmetric Transfer Hydrogenation of Simple Ketones 204

6.4.2.3 Asymmetric Transfer Hydrogenation of Functionalized Ketones 209

6.4.2.4 Asymmetric Transfer Hydrogenation of Imines 213

6.4.3 Asymmetric Transfer Hydrogenation with Biomimetic Catalysts 219

6.4.4 Asymmetric Transfer Hydrogenation with Immobilized Catalysts 222

6.5 Role of Water 228

6.5.1 Coordination to Metals 228

6.5.2 Acid–Base Equilibrium 229

6.5.3 H–D Exchange 230

6.5.4 Participation in Transition States 231

6.6 Concluding Remarks 232

References 233

7 Catalytic Rearrangements and Allylation Reactions in Water 243
Victorio Cadierno, Joaqu´•n Garc´•a-A´ lvarez, and Sergio E. Garc´•a-Garrido

7.1 Introduction 243

7.2 Rearrangements 244

7.2.1 Isomerization of Olefinic Substrates 244

7.2.1.1 Isomerization of Allylic Alcohols, Ethers, and Amines 244

7.2.1.2 Isomerization of Other Olefins 252

7.2.2 Cycloisomerizations and Related Cyclization Processes 256

7.2.3 Other Rearrangements 261

7.3 Allylation Reactions 264

7.3.1 Allylic Substitution Reactions 265

7.3.1.1 Palladium-Catalyzed Allylic Substitution Reactions (Tsuji–Trost Allylations) 265

7.3.1.2 Other Metal-Catalyzed Allylic Substitution Reactions 272

7.3.2 Allylation Reactions of C=O and C=N Bonds 273

7.3.3 Other Allylation Reactions in Aqueous Media 278

7.4 Conclusion 279

Acknowledgments 279

References 280

8 Alkene Metathesis in Water 291
Karol Grela, ®ukasz Guajski, and Krzysztof Skowerski

8.1 Introduction 291

8.1.1 General Introduction to Olefin Metathesis 291

8.1.2 Metathesis of Water-Soluble Substrates 293

8.1.3 Metathesis of Water-Insoluble Substrates 300

8.1.3.1 ‘‘Enabling Techniques’’ for Olefin Metathesis in Aqueous Media 300

8.1.3.2 Other Additives and Techniques 305

8.2 Examples of Applications of Olefin Metathesis in Aqueous Media 308

8.2.1 Polymerizations 308

8.2.2 Metathesis of Water-Soluble Substrates 312

8.2.2.1 Ring-Closing Metathesis and Enyne Cycloisomerization of Water-Soluble Substrates 312

8.2.2.2 Cross Metathesis of Water-Soluble Substrates 315

8.2.3 Cross Metathesis with Substrate Having an Allylic Heteroatom 316

8.2.4 Metathesis of Water-Insoluble Substrates 318

8.2.4.1 Ring-Closing Metathesis of Water-Insoluble Substrates 318

8.2.4.2 Enyne Cycloisomerization 328

8.2.4.3 Cross Metathesis of Water-Insoluble Substrates 328

8.3 Conclusions and Outlook 332

Acknowledgments 333

References 333

9 Nanocatalysis in Water 337
R. B. Nasir Baig and Rajender S. Varma

9.1 Introduction 337

9.2 Nanocatalysis 338

9.3 Effects of Size of Nanocatalysts 339

9.4 Transition-Metal Nanoparticles 340

9.4.1 Synthesis of Transition-Metal Nanoparticles 341

9.4.2 Greener Synthesis of Nanomaterials 341

9.4.3 Immobilization of M-NPs on a Solid Support 343

9.5 Catalytic Applications of Transition-Metal-Based Nanomaterials 343

9.6 Pd Nanoparticles in Organic Synthesis 344

9.6.1 Pd Nanoparticles in Suzuki Reactions 344

9.6.2 Pd Nanoparticles in the Heck Reactions 350

9.6.3 Pd Nanoparticles in the Sonogashira Reactions 354

9.6.4 Pd Nanoparticles in the Stille Coupling Reactions 359

9.6.5 Pd Nanoparticles in the Hiyama Couplings 360

9.6.6 Pd Nanoparticles in the Tsuji–Trost Reaction 361

9.7 Nanogold Catalysis 362

9.7.1 Coupling Reactions 362

9.7.1.1 The Suzuki–Miyaura Cross-Coupling Reaction 362

9.7.1.2 Homocoupling of Arylboronic Acid 365

9.7.2 Reduction Reactions 366

9.7.2.1 Hydrogenation of Benzene 366

9.7.2.2 Nitro group reduction 367

9.7.3 Oxidation Reactions 368

9.7.3.1 Benzylic and Allylic C–H Bonds Oxidation 368

9.7.3.2 Epoxidation of Propylene 369

9.7.3.3 Oxidation of Alcohols 370

9.7.4 Hydration of Alkynes 371

9.8 Copper Nanoparticles 372

9.8.1 Phenylselenylation of Aryl Iodides and Vinyl Bromides 372

9.8.2 Cul-Nanoparticle-Catalyzed Selective Synthesis of Phenols, Anilines, and Thiophenols 373

9.8.3 Hydrogenation of Azides over Copper Nanoparticles 373

9.8.4 Cu-Nanoparticle-Catalyzed Synthesis of Aryl Dithiocarbamate 374

9.8.5 Click Chemistry 375

9.9 Ruthenium Nanocatalysts 376

9.10 Magnetic Iron Oxide Nanoparticle 378

9.10.1 Synthesis of Heterocycles 378

9.10.2 Homocoupling of Arylboronic Acid 381

9.10.3 Rh Anchored on Fe3O4 Nanoparticles 382

9.11 Cobalt Nanoparticles 384

9.12 Conclusion 386

References 387

Index 395

See More

Pierre H. Dixneuf is Emeritus Professor of Chemistry at the University of Rennes, Bretagne, France, where he built a team working on organometallic chemistry and catalysis, and founded the Research Institute of Chemistry of Rennes. He developed several catalytic processes based on innovative ruthenium catalysts: selective transformations of alkynes and incorporation of CO2, ruthenium-vinylidenes and –allenylidenes in catalysis, catalytic synthesis of heterocycles, alkene metathesis catalysts and transformation of plant oils, C–H bond activation/functionalization including in water. He has designed new ruthenium catalysts especially involving metal-carbene bonds. He was research advisor at both CNRS and University of Rennes. He has authored/co-authored more than 400 publications, and is a member of the Institute Universitaire de France (IUF). His work has been acknowledged with several prizes including: A. v Humboldt, Le Bel, Grignard-Wittig, Sacconi medal, prix IFP of Académie des Sciences.

Victorio Cadierno received his PhD degree from the University of Oviedo (Spain) in 1996 under the supervision of Prof. J. Gimeno. He then joined the group of Dr. J. P. Majoral at the Laboratoire de Chimie de Coordination (LCC-CNRS) in Toulouse (France) for a two-year postdoctoral stay. Thereafter, he returned to the University of Oviedo where he is currently Associate Professor of Inorganic Chemistry. In 2002 he received the Young Investigator Award from the Spanish Royal Society of Chemistry (RSEQ). His research interests cover the chemistry of ruthenium complexes and their catalytic applications, with special focus on atom economical processes both in organic solvents and aqueous media. He has published more than 130 articles, reviews and book chapters in these fields.

See More

“Overall the book is recommendable to get a broad overview over state-of-the-art metal-catalyzed reaction in and on water as well as to get inspiration to improve the greenness of a process.”  (Green Processing and Synthesis, 16 October 2014)

See More

Related Titles

Back to Top