Chiral Catalyst Immobilization and Recycling

by Editor: Dirk De Vos (K. U. Leuven, Heverlee, Belgium); Editor: Ivo F. J. Vankelecom (K. U. Leuven, Heverlee, Belgium); Editor: Pierre A. Jacobs (K. U. Leuven, Heverlee, Belgium)

ISBN13: 9783527299522

ISBN10: 3527299521

Format: Hardcover

Pub. Date: 2000-12-01

Publisher(s): Wiley-VCH

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Summary

Homogeneous asymmetric catalysis offers reliable results and the possibility to 'tune' the catalysis on a rational basis. A pitfall, however, is that the separation of the catalyst from the starting material and products is difficult and often results in the loss of the catalytic material.

Immobilization offers a potential solution for the user of enantioselective catalysts in industrial processes and laboratories. Heterogeneous catalysis allows continuous operations, recycling of the catalyst, and an easy separation of the reaction products, reducing both waste and costs.

Chemists in academia and industry will welcome this careful selection of topics in this handbook that provides readers with practical and detailed information about the technical requirements for the immobilization of chiral catalysts, their application in synthesis, and methods for recycling.

Enantioselective Heterogeneous Catalysis: Academic and Industrial Challenges

(18)

Hans-Ulrich Blaser

Benoit Pugin

Martin Studer

Introduction

(1)

The Industrial Process in General and the Specific Prerequisites for Chiral Catalysts

(3)

Characteristics of the Manufacture of Enantiomerically Pure Products

(1)

Process Development: Critical Factors for the Application of (Heterogeneous) Enantioselective Catalysts

(1)

Important Criteria for Enantioselective Catalysts

(1)

The General Challenges

(2)

For Academia

(1)

For Industry

(1)

Chiral Heterogeneous Catalysts: State of the Art and Future Challenges

(9)

Heterogeneous Catalysts Modified with a Chiral Auxiliary

(1)

Metallic Catalysts on Chiral Supports

(1)

Metallic Catalysts Modified with a Low Molecular Weight Chiral Auxiliary

(1)

Metal Oxide Catalysts Modified with a Chiral Auxiliary having Low Molecular Weight

(1)

Immobilized and Functionalized Homogeneous Catalysts

(1)

Immobilized Homogeneous Catalysts

(2)

Alternative Methods Using Functionalized Ligands

(2)

Catalysts with No Known Heterogeneous or Homogeneous Precedent

(1)

Insoluble Polypeptides and Gels

(1)

Artificial Catalytic Antibodies

(1)

Conclusions

(4)

References

(4)

Catalyst Immobilization on Inorganic Supports

(24)

Ivo F.J. Vankelecom

Pierre A. Jacobs

Introduction

(1)

General Considerations

(2)

Supports

(1)

Improved Activity of Heterogeneous Complexes

(6)

Practical Examples

(15)

Covalent Attachment

(5)

Adsorption or Ion-Pair Formation

(3)

Encapsulation

(1)

Entrapment

(1)

Supported Liquid Phase (SLP)

(1)

Modification of an Achiral Heterogeneous Catalyst with a Chiral Auxiliary

(1)

Achiral Metal Catalysts on Chiral Supports

(1)

References

(2)

Organic Polymers as a Catalyst Recovery Vehicle

(38)

David E. Bergbreiter

General Introduction

(4)

Alkene Hydrogenation

(7)

Carbonyl and Imine Reduction

(6)

Carbon-Carbon Bond Formation

(4)

Carbonyl Alkylation

(3)

Diels-Alder Reactions

(3)

Enolate Chemistry

(1)

Strecker Chemistry

(1)

Asymmetric Dihydroxylation

(3)

Epoxidation and Epoxide Ring Opening

(3)

Acylation Catalysts

(1)

Conclusion

(3)

References

(3)

Liquid Biphasic Enantioselective Catalysis

(16)

Brian E. Hanson

Introduction

(2)

Hydrogenation

(6)

Hydroformylation

(2)

Oxidation

(1)

Lewis Acid-Catalyzed Reactions

(1)

Enzymatic Reactions

(1)

Summary

(3)

References

(2)

Immobilized Enzymes in Enantioselective Organic Synthesis

(26)

Peter Rasor

Introduction

(2)

Immobilization

(11)

Methods of Immobilization

100

(1)

Enzymes

101

(1)

Carriers

102

(3)

Binding Enzymes to Carriers

105

(1)

Cross-Linked Enzyme Crystals

106

(1)

Activity Assay

107

(2)

Activity Balance

109

(1)

Cost of Immobilization

110

(1)

Operation

110

(10)

Reactors

113

(2)

Operational Stability

115

(5)

Summary

120

(3)

References

121

(2)

Enantioselective Hydrogenation Catalyzed by Platinum Group Metals Modified by Natural Alkaloids

123

(32)

Peter B. Wells

Richard P.K. Wells

Historical Perspective

123

(1)

Enantioselective Hydrogenation of Activated Ketones over Platinum

124

(6)

Mechanisms of Enantioselective Pyruvate Hydrogenation over Platinum

130

(9)

The Adsorption Model

130

(7)

The Chemical Shielding Model

137

(2)

Enantioselective Hydrogenation of Activated Ketones over Palladium

139

(2)

Enantioselective Hydrogenation of Substituted Alkenes over Palladium

141

(4)

Enantioselective Hydrogenation Involving Carbon-Nitrogen Unsaturation

145

(3)

Enantioselectivity Induced by Other Families of Alkaloids

148

(3)

Conclusion

151

(4)

References

152

(3)

Design of New Chiral Modifiers for Heterogeneous Enantioselective Hydrogenation: A Combined Experimental and Theoretical Approach

155

(18)

Alfons Baiker

Introduction

155

(1)

Chiral Modification of Metal Catalysts

156

(1)

Prerequisities for Rational Design of Chiral Modifiers

156

(1)

A Case Study -- Chiral Modification of Platinum by Cinchona Alkaloids

157

(12)

Experimental Findings

157

(5)

Theoretical Studies

162

(2)

Design of New Modifiers

164

(5)

Conclusions and Outlook

169

(4)

References

170

(3)

Modified Ni Catalysts for Enantioselective Hydrogenation

173

(38)

Akira Tai

Takashi Sugimura

Introduction

173

(1)

General Characteristics of MNi

174

(9)

Variables Affecting the Enantiodifferentiating Ability (e.d.a.) of MNi

174

(1)

Modification Variables

174

(1)

Variables Concerning the Preparation of the Ni Catalyst

175

(5)

Substrate and Hydrogenation Parameters

180

(1)

Kinetics of Hydrogenation over MNi

181

(1)

State of the Adsorbed TA

182

(1)

Elucidation of the Mechanism of MRNi and Development of a Highly Efficient MRNi Catalyst Based on Hypothetical Models

183

(28)

Enantiodifferentiating and Non-Enantiodifferentiating Regions on MNi

184

(1)

The Catalyst Region Model

184

(2)

Enhancement of the e.d.a. of MRNi

186

(4)

Catalytic Stability of MRNi

190

(2)

Enantiodifferentiation and Hydrogenation Steps in the Reaction Path (Reaction Process Model)

192

(1)

Interaction between Substrate and TA on MNi (Stereochemical Model)

193

(1)

Stereochemical Model Based on the Interaction between TA and MAA through Two Hydrogen Bonds (2P Model)

193

(6)

Stereochemical Model Based on the Interaction between TA and Methyl Alkyl Ketones through One Hydrogen Bond and a Steric Repulsion (1P Model)

199

(3)

Extended Stereochemical Model: Merging the 2P and 1P Models

202

(5)

Conclusions of the Model Studies

207

(1)

References

208

(3)

Catalytic Hydrogenation, Hydroformylation and Hydrosilylation with Immobilized P- and N-Ligands

211

(24)

Daniel J. Bayston

Mario E.C. Polywka

Introduction

211

(1)

Asymmetric Hydrogenation with Immobilized Catalysts

212

(15)

Immobilized DIOP Derivatives

212

(3)

Immobilized BPPM Derivatives

215

(3)

Immobilized BINAP Derivatives

218

(3)

Immobilization of Catalysts on Cation-Exchange Resins

221

(2)

Transfer Hydrogenation with Immobilized Catalysts

223

(2)

Other Immobilized Ligands for Asymmetric Hydrogenation

225

(2)

Enantioselective Hydroformylation with Immobilized Catalysts

227

(5)

Immobilized DIOP Derivatives

227

(2)

Immobilized BPPM Derivatives

229

(1)

Immobilized Phosphine-Phosphite Derivatives

230

(2)

Catalytic Asymmetric Hydrosilylation with Immobilized Ligands

232

(1)

Conclusions

233

(2)

References

233

(2)

Catalytic Heterogeneous Enantioselective Dihydroxylation and Epoxidation

235

(26)

P. Salvadori

D. Pini

A. Petri

A. Mandoli

Introduction

235

(1)

Asymmetric Dihydroxylation

235

(11)

Use of Functionalized Polymers: Insoluble Polymer-Bound Catalysts for AD (IPB-AD)

237

(7)

Use of Inorganic Supports

244

(2)

Heterogeneous Catalytic Asymmetric Epoxidation of Carbon-Carbon Double Bonds

246

(10)

Epoxidation of Unfunctionalized Alkenes with Mn(salen) Catalysts

247

(1)

Organic Insoluble Polymer-Bound Jacobsen-Type Catalysts (IPB-AE)

247

(5)

Inorganic Polymer-Supported Jacobsen-Type Catalysts

252

(2)

Epoxidation of Allylic Alcohols with Sharpless-Type Ti Catalysts

254

(1)

Epoxidation of a,β-Unsaturated Ketones under Julia-Colonna Conditions

255

(1)

Conclusions

256

(5)

References

257

(4)

Enantioselective C-C Bond Formation with Heterogenized Catalysts

261

(22)

S. Abramson

N. Bellocq

D. Brunel

M. Lasperas

P. Moreau

Introduction

261

(5)

Enantioselective Alkylation of Aldehydes by Organozinc Reagents with Immobilized Catalysts

266

(11)

Heterogenization of Chiral Aminoalcohols on Polymeric Supports

266

(6)

Heterogenization of TADDOLates and Binaphthols on Polymeric Supports

272

(1)

Heterogenization of Chiral Ligands on Mineral Supports

273

(1)

Immobilization on Alumina and Silica Gel

274

(1)

Immobilization on Zeolites

274

(1)

Immobilization in Micelle-Templated Silicas (MTS)

275

(2)

Diels-Alder Reactions with Immobilized Catalysts

277

(6)

Heterogenization of Chiral Lewis Acids on Polymers

277

(3)

Heterogenization of Chiral Lewis Acids on Mineral Supports

280

(1)

References

280

(3)

Heterogeneous Diastereoselective Catalysis

283

(24)

Dirk E. de Vos

Mario De bruyn

Vasile I. Parvulescu

Florian G. Cocu

Pierre A. Jacobs

Introduction

283

(1)

Diastereoselective Heterogeneously Catalyzed Reactions

284

(23)

Hydrogenations

284

(1)

Hydrogenation of C=C Bonds

284

(6)

Hydrogenation of C=N Bonds

290

(3)

Hydrogenation of C=O Bonds

293

(1)

Hydrogenation of Aromatics

294

(2)

Hydrogenation of Heterocyclic Compounds

296

(3)

Miscellaneous Reactions

299

(1)

Hydrogenolysis

299

(1)

Pd-Catalyzed Cyclizations

299

(1)

Diels-Alder Cycloadditions

300

(1)

Stereoselective Protonation of Enolates

301

(1)

Thio-Claisen Rearrangement

301

(1)

Epoxidation and Subsequent Epoxide Rearrangement

302

(3)

References

305

(2)

Index

307

Chiral Catalyst Immobilization and Recycling

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