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
• Copyright: 2000-12-01
• Publisher: Wiley-VCH

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.

Table of Contents

Enantioselective Heterogeneous Catalysis: Academic and Industrial Challenges	1	(18)
Hans-Ulrich Blaser
Benoit Pugin
Martin Studer
Introduction	1	(1)
The Industrial Process in General and the Specific Prerequisites for Chiral Catalysts	1	(3)
Characteristics of the Manufacture of Enantiomerically Pure Products	2	(1)
Process Development: Critical Factors for the Application of (Heterogeneous) Enantioselective Catalysts	2	(1)
Important Criteria for Enantioselective Catalysts	3	(1)
The General Challenges	4	(2)
For Academia	5	(1)
For Industry	5	(1)
Chiral Heterogeneous Catalysts: State of the Art and Future Challenges	6	(9)
Heterogeneous Catalysts Modified with a Chiral Auxiliary	6	(1)
Metallic Catalysts on Chiral Supports	6	(1)
Metallic Catalysts Modified with a Low Molecular Weight Chiral Auxiliary	7	(1)
Metal Oxide Catalysts Modified with a Chiral Auxiliary having Low Molecular Weight	8	(1)
Immobilized and Functionalized Homogeneous Catalysts	9	(1)
Immobilized Homogeneous Catalysts	9	(2)
Alternative Methods Using Functionalized Ligands	11	(2)
Catalysts with No Known Heterogeneous or Homogeneous Precedent	13	(1)
Insoluble Polypeptides and Gels	13	(1)
Artificial Catalytic Antibodies	14	(1)
Conclusions	15	(4)
References	15	(4)
Catalyst Immobilization on Inorganic Supports	19	(24)
Ivo F.J. Vankelecom
Pierre A. Jacobs
Introduction	19	(1)
General Considerations	19	(2)
Supports	21	(1)
Improved Activity of Heterogeneous Complexes	22	(6)
Practical Examples	28	(15)
Covalent Attachment	28	(5)
Adsorption or Ion-Pair Formation	33	(3)
Encapsulation	36	(1)
Entrapment	37	(1)
Supported Liquid Phase (SLP)	38	(1)
Modification of an Achiral Heterogeneous Catalyst with a Chiral Auxiliary	39	(1)
Achiral Metal Catalysts on Chiral Supports	40	(1)
References	41	(2)
Organic Polymers as a Catalyst Recovery Vehicle	43	(38)
David E. Bergbreiter
General Introduction	43	(4)
Alkene Hydrogenation	47	(7)
Carbonyl and Imine Reduction	54	(6)
Carbon-Carbon Bond Formation	60	(4)
Carbonyl Alkylation	64	(3)
Diels-Alder Reactions	67	(3)
Enolate Chemistry	70	(1)
Strecker Chemistry	71	(1)
Asymmetric Dihydroxylation	71	(3)
Epoxidation and Epoxide Ring Opening	74	(3)
Acylation Catalysts	77	(1)
Conclusion	78	(3)
References	78	(3)
Liquid Biphasic Enantioselective Catalysis	81	(16)
Brian E. Hanson
Introduction	81	(2)
Hydrogenation	83	(6)
Hydroformylation	89	(2)
Oxidation	91	(1)
Lewis Acid-Catalyzed Reactions	92	(1)
Enzymatic Reactions	93	(1)
Summary	94	(3)
References	95	(2)
Immobilized Enzymes in Enantioselective Organic Synthesis	97	(26)
Peter Rasor
Introduction	97	(2)
Immobilization	99	(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