Description
Wiley Aqueous-phase Organometallic Catalysis Concepts and Applications 2004 Edition by Boy Cornils, Wolfgang A. Herrmann
This work is now in its second completely revised and expanded edition. Written by the renowned editors B. Cornils and W. A. Herrmann, this book presents every important aspect of aqueous-phase organometallic catalysis, a method which saves time, waste and money. The large-scale application of this 'green' technology in chemical industry clearly underlines its practical use outside of academia. New chapters (for example 'Organic Chemistry in Water'), 20 per cent more content and fully updated contributions from a plethora of international authors make this book a 'must-have' for everyone working in this field. From the reviews of the first edition: 'This overview will be extremely useful for everyone active in this field [...]' - "Angewandte Chemie". 'This book is an essential in any chemical research library and I strongly recommend it to all synthetic research and teaching chemists. [...]' - "The Alchemist". 'The editors are to be congratulated on assembling such a wide range of contributors who have described the industrial as well as the academic aspects of the subject' - "Journal of Organometallic Chemistry". Table of contents :- 1 Introduction.1 Introduction (B. Cornils, W.A. Herrmann).2 Basic Aqueous Chemistry.2.1 Organic Chemistry in Water (A. Lubineau, J. Auge, M.-C. Scherrmann).2.1.1 Introduction.2.1.2 Origin of the Reactivity in Water.2.1.3 Pericyclic Reactions.2.1.3.1 Diels - Alder Reactions.2.1.3.2 Hetero Diels -Alder Reactions.2.1.3.3 Other Cycloadditions.2.1.3.4 Claisen Rearrangements.2.1.4 Carbonyl Additions.2.1.4.1 Aldol-type Reactions.2.1.4.2 Michael-type Reactions.2.1.4.3 Allylation Reactions.2.1.5 Oxido-reductions.2.1.5.1 Oxidations.2.1.5.2 Reductions.2.1.6 Radical Reactions.2.1.7 Outlook.2.2 Organometallic Chemistry in Water (W.A. Herrmann, F.E. Kuhn).2.2.1 Introduction.2.2.2 Water as a Solvent and Ligand.2.2.3 Organometallic Reactions of Water.2.2.4 Catalytic Reactions with Water.2.2.4.1 Water-gas Shift Reaction.2.2.4.2 Wacker- Hoechst Acetaldehyde Process.2.2.4.3 Olefin Hydration.2.2.4.4 Hydrodimerization.2.2.5 Water-soluble Metal Complexes.2.2.6 Perspectives.2.3 Characterization of Organometallic Compounds in Water (G. Laurenczy).2.3.1 Introduction.2.3.2 General Survey.2.3.3 Effect of High Hydrostatic Pressure on Aqueous Organometallic Systems.2.3.4 Aqueous Organometallics with Pressurized Gases.2.3.5 Concluding Remarks.3 Catalysts for an Aqueous Catalysis.3.1 Variation of Central Atoms.3.1.1 Transition Metals (D.J. Darensbourg, C.G. Ortiz).3.1.1.1 Introduction.3.1.1.2 Water-soluble Catalysts by Virtue of Water-soluble Ligands.3.1.1.3 Water-soluble Catalysts through Water Coordination.3.1.2 Lanthanides in Aqueous-phase Catalysis (S. Kobayashi).3.1.2.1 Introduction.3.1.2.2 Aldol Reactions.3.1.2.3 Mannich-type Reactions.3.1.2.4 Diels - Alder Reactions.3.1.2.5 Micellar Systems.3.1.2.6 Asymmetric Catalysis in Aqueous Media.3.1.2.7 Conclusions.3.2 Variation of Ligands.3.2.1 Monophosphines (O. Stelzer+, S. Rossenbach, D. Hoff).3.2.1.1 General Features, Scope, and Limitations.3.2.1.2 Anionic Phosphines.3.2.1.3 Cationic Phosphines.3.2.1.4 Nonionic Water-soluble Phosphines.3.2.2 Diphosphines and Other Phosphines (M. Schreuder Goedheijt, P.C.J. Kamer, J.N.H. Reek, P.W.N.M. van Leeuwen).3.2.2.1 General.3.2.2.2 Diphosphines - Introduction of Sulfonate Groups by Direct Sulfonation.3.2.2.3 Introduction of Sulfonate Groups During Synthesis.3.2.2.4 Diphosphines with Quaternized Aminoalkyl or Aminoaryl Groups.3.2.2.5 Diphosphines with Hydroxyalkyl or Polyether Substituents.3.2.2.6 Carboxylated Diphosphines.3.2.2.7 Amphiphilic Diphosphines.3.2.2.8 Other Phosphines.3.2.3 Ligands or Complexes Containing Ancillary Functionalities (P. Kalck, M. Urrutigoity).3.2.3.1 Complexes Containing at Least Two Classical Functionalities.3.2.3.2 Cationic Complexes.3.2.3.3 Immobilization on Silica Supports.3.2.3.4 Macromolecular Ligands or Supports.3.2.3.5 Ligands not Containing Phosphorus.3.2.3.6 Additional Perspectives.3.2.4 Tenside Ligands (G. Papadogianakis).3.2.4.1 Introduction.3.2.4.2 Tenside Phosphines and Amines.3.2.4.3 Hydroformylation Reactions Catalyzed by Transition Metal Surfactant -Phosphine Complexes.3.2.4.4 Hydrogenation Reactions Catalyzed by Transition Metal Surfactant -Phosphine Complexes.3.2.4.5 Carbonylation Reactions Catalyzed by Transition Metal Surfactant -Phosphine Complexes.3.2.4.6 Concluding Remarks and Future Prospects.3.2.5 Chiral Ligands (W.A. Herrmann, R.W. Eckl, F.E. Kuhn).3.2.5.1 Introduction.3.2.5.2 Sulfonated Chiral Phosphines.3.2.5.3 Other Water-soluble Chiral Ligands.3.2.5.4 Conclusions.3.2.6 Other Concepts (A. Borner).3.2.6.1 Hydroxyphosphines as Ligands.3.2.6.2 Amines and Polyoxometallates as Ligands (W.A. Herrmann, C.-P. Reisinger).4 Catalysis in Water as a Special Unit Operation.4.1 Fundamentals of Biphasic Reactions in Water (Y.Onal, M. Baerns, P. Claus).4.1.1 Introduction.4.1.2 Gas/Liquid-phase Reactions.4.1.3 Gas/Liquid/Liquid-phase Reactions.4.1.4 Place of Reaction in Aqueous Biphasic Systems.4.2 Technical Concepts (A. Behr).4.2.1 Reaction Systems.4.2.2 Technical Realization: Variations.4.2.2.1 Reaction with Product Separation.4.2.2.2 Reaction and Product Extraction.4.2.2.3 Reaction and Product Treatment.4.2.2.4 Reaction and Catalyst Separation.4.2.2.5 Reaction and Catalyst Extraction.4.2.2.6 Reaction and Catalyst Treatment.4.2.3 Reaction Engineering Aspects.4.2.4 New Developments.4.2.4.1 Telomerization.4.2.4.2 Oligomerization.4.2.4.3 Hydrogenation.4.2.4.4 Hydroformylation.4.2.4.5 Other Reactions.4.3 Side Effects, Solvents, and Co-solvents (B.E. Hanson).4.3.1 Introduction.4.3.2 Hydroformylation.4.3.3 Hydrogenations and Other Catalytic Reactions.4.4 Membrane Techniques (H. Bahrmann, B. Cornils).4.5 Micellar Systems (G. Oehme).4.5.1 Introduction.4.5.2 Hydrolytic Reactions in Micelles.4.5.3 Oxidation Reactions in Micelles.4.5.4 Complex-catalyzed Hydrogenation in Micellar Media.4.5.5 Carbon -Carbon Coupling Systems.4.5.6 Some Examples of Reactions in Reverse Micelles and Microemulsions.4.5.7 Perspectives.4.6 On the Borderline of Aqueous-phase Catalysis.4.6.1 Phase-transfer Catalysis (E.V. Dehmlow).4.6.1.1 General Overview, Fundamentals, and Definitions.4.6.1.2 Aqueous Organic-phase Heck and Other Cross Couplings under Phase-transfer Catalysis Conditions.4.6.1.3 Hydrogenations Mediated by Phase-transfer Catalysts.4.6.1.4 Biphasic Transfer Hydrogenations.4.6.1.5 Aqueous/Organic-phase Oxidations Mediated by Metal and PT Catalysts.4.6.1.6 Aqueous/Organic-phase Carbonylations.4.6.2 Counter-phase Transfer Catalysis (T. Okano).4.6.2.1 Introduction.4.6.2.2 Mechanism of the Counter-phase Transfer Catalytic Reaction.4.6.2.3 Counter-phase Transfer Catalytic Reactions.4.6.2.4 Concluding Remarks.4.6.3 Thermoregulated Phase-transfer and Thermoregulated Phase-separable Catalysis (Z. Jin, Y. Wang, X. Zheng).4.6.3.1 Introduction.4.6.3.2 Thermoregulated Phase-transfer Catalysis with Nonionic Water-soluble Phosphines.4.6.3.3 Hydroformylation of Higher Alkenes Based on TRPTC.4.6.3.4 Thermoregulated Phase-separable Catalysis.4.6.3.5 Conclusions.4.7 Transitions to Heterogeneous Techniques (SAPC and Variations) (M.E. Davis).4.7.1 Introduction.4.7.2 The SAPC Concept of Immobilization.4.7.3 Example of Rational Catalyst Design Strategy.4.7.4 Suggested Reactions for Implementation of Design Concepts.4.7.5 Outlook.5 Aqueous Catalysts for Environment and Safety.5.1 Water-soluble Organometallics in the Environment (W.A. Herrmann, F.E. Kuhn).5.1.1 Introduction.5.1.2 Biological Methylation.5.1.3 Cobalamines - Organometallics in Nature.5.1.4 Organoarsenic and Organotin Compounds.5.1.5 Organomercury Compounds.5.1.6 Other Metal-alkyl Complexes in the Environment.5.1.7 Perspectives.5.2 Environmental and Safety Aspects (B. Cornils, E. Wiebus).5.2.1 Introduction.5.2.2 The Ruhrchemie/Rho ne-Poulenc (RCH/RP) Process.5.2.3 Crucial Environmental Improvements.5.2.4 Conclusions.6 Typical Reactions.6.1 Hydroformylation 3516.1.1 Development of the Commercial Biphasic Oxo Synthesis (B. Cornils, E.G. Kuntz).6.1.1.1 History of Biphasic Catalysis.6.1.1.2 Basic Work and Investigations by Rhone-Poulenc.6.1.1.3 Investigations by Ruhrchemie AG.6.1.1.4 The RCH/RP Process as the Final Point of Development.6.1.2 Kinetics (R.V. Chaudhari, B.M. Bhanage).6.1.2.1 Introduction.6.1.2.2 Kinetics Using Water-soluble Catalysts.6.1.2.3 Concluding Remarks.6.1.3 Reaction of Alkenes.6.1.3.1 Lower Alkenes (C.D. Frohning, C.W. Kohlpaintner).6.1.3.2 Higher Alkenes (H. Bahrmann, S. Bogdanovic, P.W.N.M. van Leeuwen).6.1.3.3 Functionalized Alkenes (E. Monflier, A. Mortreux).6.1.4 Re-immobilization Techniques (H. Bahrmann).6.1.4.1 Introduction.6.1.4.2 Water-insoluble, Re-immobilized Liphophilic Ligands and Their Separation by Membrane Technique.6.1.4.3 Separation and Use of Water-insoluble Ammonium Ligands in Hydroformylation.6.1.4.4 Separation of Phosphine Oxides and Other Degradation Products.6.1.4.5 Further Developments.6.2 Hydrogenation (F. Joo, A. Katho).6.2.1 Introduction.6.2.2 Mechanisms and Catalysts of Hydrogenations in Aqueous Solution.6.2.2.1 Basic Mechanisms of Dihydrogen Activation.6.2.2.2 Water-soluble Hydrogenation Catalysts with Tertiary Phosphine Ligands.6.2.2.3 Complexes of Ligands with Donor Atoms Other Than Phosphorus(III ).6.2.3 Typical Reactions.6.2.3.1 Hydrogenation of Compounds with C=C and C C Bonds.6.2.3.2 Hydrogenation of Compounds with C=O and C=N Bonds.6.2.3.3 Hydrogenolysis of C-O, C-N, C-S, and C-Halogen Bonds.6.2.3.4 Miscellaneous Hydrogenations.6.3 Hydrogenation and Hydrogenolysis of Thiophenic Molecules (C. Bianchini, A. Meli).6.3.1 Introduction.6.3.2 Hydrogenation Reactions.6.3.3 Hydrogenolysis Reactions.6.3.4 Future Developments.6.4 Oxidations.6.4.1 Partial Oxidations (R.A. Sheldon, G. Papadogianakis).6.4.1.1 Introduction.6.4.1.2 Water-soluble Ligands.6.4.1.3 Concluding Remarks.6.4.2 Wacker-type Oxidations (E. Monflier, A. Mortreux).6.4.2.1 Possibilities of Wacker-type Oxidations.6.4.2.2 Conclusions.6.4.3 Methyltrioxorhenium(VII) as an Oxidation Catalyst (F.E. Kuhn, W.A. Herrmann).6.4.3.1 Introduction.6.4.3.2 Synthesis of Methyltrioxorhenium(VII).6.4.3.3 Behavior of Methyltrioxorhenium in Water.6.4.3.4 Catalyst Formation and Applications in Alkene Epoxidation.6.4.3.5 Other Oxidation Reactions.6.4.3.6 Perspectives.6.5 Carbonylation Reactions (M. Beller, J.G.E. Krauter).6.5.1 Introduction.6.5.2 Reductive Carbonylations.6.5.3 Carboxylation of C-X Derivatives.6.5.4 Hydrocarboxylation of Alkenes.6.5.5 Conclusions.6.6 C-C Coupling Reactions (Heck, Stille, Suzuki, etc.) (W.A. Herrmann, C.-P. Reisinger, P. Harter).6.6.1 Introduction.6.6.2 Catalysts and Reaction Conditions.6.6.3 Olefination.6.6.4 Alkyne Coupling.6.6.5 Cross-coupling Reactions.6.6.5.1 Suzuki Coupling.6.6.5.2 Stille Coupling.6.6.5.3 Miscellaneous.6.6.6 Conclusions.6.7 Hydrocyanation (H.E. Bryndza, J.A. Harrelson, Jr.).6.7.1 Introduction.6.7.2 HCN as a Synthon.6.7.2.1 Michael Additions of HCN to Activated Alkenes.6.7.2.2 Synthesis of Cyanohydrins from Ketones and Aldehydes.6.7.2.3 Strecker Synthesis of Aminonitriles.6.7.2.4 HCN Addition to Unactivated C-C Double Bonds.6.7.2.5 Cyanide Coupling Reactions.6.7.3 Summary.6.8 Allylic Substitution (D. Sinou).6.8.1 Introduction.6.8.2 Scope of the Reaction.6.8.3 Applications.6.8.4 Conclusions.6.9 Hydrodimerization (N. Yoshimura).6.9.1 Introduction.6.9.2 Development of Technologies.6.9.3 Process of the Manufacture of 1-Octanol and Other Derivatives.6.9.4 Applications.6.10 Alkene Metathesis (R.H. Grubbs, D.M. Lynn).6.10.1 Introduction.6.10.2 "Classical" Group VIII Catalysts.6.10.3 Polymers Prepared via Aqueous ROMP.6.10.4 Alkylidenes as Catalysts.6.10.4.1 Well-defined Ruthenium Alkylidenes.6.10.4.2 Water-soluble Alkylidenes.6.10.5 Summary.6.11 Asymmetric Synthesis (D. Sinou).6.12 Catalytic Polymerization (S. Mecking).6.12.1 Introduction.6.12.2 Copolymerization of Carbon Monoxide with Alkenes.6.12.3 Polymerization of Ethylene and 1-Alkenes.6.12.4 Polymerization of Conjugated Dienes.6.12.5 Vinyl-type Polymerization of Cyclic Alkenes.6.12.6 Ring Opening Metathesis Polymerization.6.12.7 Polymerization of Alkynes.6.12.8 Polymerization by Suzuki Coupling.6.12.9 Summary and Outlook.6.13 Oleochemistry (A. Behr).6.13.1 Introduction.6.13.2 Hydrogenation.6.13.3 Hydroformylation.6.13.4 Hydrocarboxylation.6.13.5 Oxidation.6.13.6 Oligomerization.6.13.7 Hydrosilylation.6.13.8 Isomerization.6.14 Halogen Chemistry (M. Bressan, A. Morvillo).6.14.1 Introduction.6.14.2 Reductive and Oxidative Dehalogenation.6.14.3 Coupling and Carbonylation Reactions.6.15 Biological Conversions (P.J. Quinn).6.15.1 Introduction.6.15.2 Biological Substrates.6.15.3 Hydrogenation of Unsaturated Lipids in Aqueous Dispersions.6.15.3.1 Water-insoluble Homogeneous Catalysts.6.15.3.2 Water-soluble Homogeneous Catalysts.6.15.3.3 Sources of Hydrogen.6.15.4 Hydrogenation of Biological Membranes.6.15.4.1 Topology of Unsaturated Lipids in Membranes.6.15.4.2 Function of Unsaturated Lipids in Membranes.6.15.4.3 Acclimation of Membranes to Low Temperature.6.15.4.4 Membrane Unsaturation and Stability at High Temperatures.6.15.4.5 Biochemical Homeostasis of Unsaturated Lipids.6.15.4.6 Hydrogenation of Living Cells.6.15.5 Conclusions.6.16 Other Recent Examples (W.A. Herrmann, A.M. Santos, F.E. Kuhn).6.16.1 Introduction.6.16.2 Isomerizations.6.16.3 Aldolizations.6.16.4 Hydroaminomethylation.6.15.5 Aminations.6.16.6 Hydrosilylations.6.16.7 Thiolysis.6.16.8 Synthesis of Various Heterocycles.7 Other Biphasic Concepts.7.1 Nonaqueous Organic/Organic Separation (SHOP Process) (D. Vogt).7.1.1 Introduction.7.1.2 Process Description.7.2 Catalysis in Fluorous Phases ( J.T. Horva-th).7.2.1 Introduction.7.2.2 The Fluorous Concept.7.2.3 Process and Applications.7.3 Nonaqueous Ionic Liquids (ILs, NAILs) (H. Olivier-Bourbigou).7.3.1 Introduction.7.3.2 NAILs as a New Class of Solvents.7.3.3 Applications in Organic Synthesis and Catalysis.7.3.3.1 Salts Containing Strongly Coordinating Anions to Stabilize Anionic Complexes.7.3.3.2 Salts Containing Weakly Coordinating Anions for Cationic and Molecular Complexes.7.3.3.3 Salts Containing Chloroaluminate Anions as Solvents and Acidic Catalysts.7.3.3.4 Supported Ionic Liquid Catalysis.7.3.3.5 Solvents for Organic Reactions.7.3.4 Concluding Remarks.7.4 Immobilization of Organometallic Catalysts Using Supercritical Fluids (W. Leitner, A.M. Scurto).7.4.1 Introduction.7.4.2 Practical Approaches to Multiphase Catalysis Involving Supercritical Fluids.7.4.2.1 Supercritical Fluids and Supported Catalysts.7.4.2.2 Liquid/Supercritical Biphasic Systems.7.4.2.3 Catalysis and Extraction Using sc Solutions (CESS).7.4.3 Conclusions and Outlook.7.5 The Amphiphilic Approach (P.C.J. Kamer, J.N.H. Reek, P.W.N.M. van Leeuwen).7.5.1 Separation Methods.7.5.1.1 Two-phase Catalysis.7.5.1.2 The Extraction Concept.7.5.2 Use of Amphiphilic Phosphines.7.5.2.1 Catalysis Using Amphiphilic Ligands.7.5.2.2 Distribution Characteristics of the Free Ligands.7.5.2.3 Rhodium Recycling.7.5.3 Conclusions.7.6 Catalysis with Water-soluble Polymer-bound Ligands in Aqueous Solution (S. Mecking, E. Schwab).7.6.1 Introduction.7.6.2 Catalysis with Water-soluble Polymer-bound Ligands in Aqueous Solutionshow more