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Categories: Organic Chemistry >> Synthesis >> Transition Metals

Recoverable and Recyclable Catalysts

Maurizio Benaglia

Hardcover, 500 Pages
First Edition, 2009
ISBN: 978-0-470-68195-4
Wiley

Description

There is continued pressure on chemical and pharmaceutical industries to reduce chemical waste and improve the selectivity and efficiency of synthetic processes. The need to implement green chemistry principles is a driving force towards the development of recoverable and recyclable catalysts.

The design and synthesis of recoverable catalysts is a highly challenging interdisciplinary field combining chemistry, materials science engineering with economic and environmental objectives. Drawing on international research and highlighting recent developments, this book serves as a practical guide for both experts and newcomers to the field.

Each chapter combines principles with practical information on the synthesis of catalysts and strategies for catalyst recovery. The book concludes with a comparison of different catalytic systems, using case studies to illustrate the key features of each approach.

Editorial Review

According to green chemistry principles, catalyzed reactions are often better than their uncatalyzed versions. Not only the ecological, but also the economic profile is further improved if the catalyst is recyclable. This brings to mind precious transition metal complexes, which in pharmaceutical production also contaminate the product with heavy metals. Recyclability can either be achieved when the catalyst is bound to a solid phase, or when its solubility characteristics are modified so that it can readily be separated from the product by extraction during work-up.

The book begins with an introduction by John Gladysz, which explains all the important fundamentals. Gladysz adds a cautionary note, explaining that the recyclability implied by good yields in subsequent runs with recycled catalyst is often bogus. Thus, when a reaction is completed in five minutes under catalysis while the yield is only determined after one hour, complete conversions can still be achieved in subsequent runs with the catalyst even if its activity drops by half. These words come to mind when clean yields are alluded to time and again in the subsequent chapters.

The specific chapters cover a broad spectrum of topics with relatively little overlap, and are well crafted. The introductions within the chapters often span several pages, and are readily understandable and quite well illustrated, which helps to convey the basics of the corresponding method. The subsequent sections list dozens of examples of specific conversions, one or the other of which are ready to inspire ideas. Working through this book, the reader gains an excellent overview of all the methods for preparing recyclable catalysts, and once one has decided on a specific method, each chapter contains countless citations to the literature.

In this respect, "Recoverable and Recyclable Catalysts" is a substantial resource for those who do process development and scale-up work. Since it moreover offers a body of background knowledge, it is also highly recommended for advanced students who are interested in catalysis and green methods.

Contents

1 The Experimental Assay of Catalyst Recovery: General Concepts (John A. Gladysz).
1.1 Introduction.
1.2 Catalyst Precursor vs Catalyst.
1.3 Catalyst vs Catalyst Resting State.
1.4 Catalyst Inventory: Loss Mechanisms.
1.5 Evaluation of Catalyst Recovery.
1.6 Prospective.
References.

2 Surface-functionalized Nanoporous Catalysts for Renewable Chemistry (Brian G. Trewyn, Hung-Ting Chen and Victor S.-Y. Lin).
2.1 Introduction.
2.2 Immobilization Strategies of Heterogeneous Catalysts.
2.3 Efficient Heterogeneous Catalysts with Enhanced Reactivity and Selectivity with Functionality.
2.4 Other Heterogeneous Catalyst Systems on Nonsilica Supports.
2.5 Conclusion.
References.

3 Insoluble Resin-supported Catalysts (Gang Zhao and Zhuo Chai).
3.1 Introduction.
3.2 Transition Metal Catalyzed C_C Bond Formation Reactions.
3.3 Oxidation.
3.4 Reduction.
3.5 Organocatalyzed Reactions.
3.6 Annulation Reactions.
3.7 Miscellaneous.
3.8 Conclusion.
References.

4 Catalysts Bound to Soluble Polymers (Tamilselvi Chinnusamy, Petra Hilgers and Oliver Reiser).
4.1 Introduction.
4.2 Soluble Supports – General Considerations.
4.3 Recent Developments of Soluble Polymer-supported Catalysts.
4.4 Recent Examples for Reactions Promoted by Catalysts Bound to Soluble Polymers.
4.5 Conclusion.
List of Abbreviations.
References.

5 Polymeric, Recoverable Catalytic Systems (Qiao-Sheng Hu).
5.1 Introduction.
5.2 Polymeric Catalyst Systems.
5.3 Summary.
Acknowledgements.
References.

6 Thermomorphic Catalysts (David E. Bergbreiter).
6.1 Introduction.
6.2 Thermomorphic Catalyst Separation Strategies.
6.3 Hydrogenation Reactions Under Thermomorphic Conditions.
6.4 Hydroformylation Reactions Under Thermomorphic Conditions.
6.5 Hydroaminations Under Thermomorphic Conditions.
6.6 Pd-catalyzed Reactions Under Thermomorphic Conditions.
6.7 Polymerization Reactions Under Thermomorphic Conditions.
6.8 Organocatalysis Under Thermomorphic Conditions.
6.9 Cu(I)-catalyzed 1,3-Dipolar Cycloadditions Under Thermomorphic Conditions.
6.10 Thermomorphic Hydrosilylation Catalysts.
6.11 Thermomorphic Catalytic Oxidations.
6.12 Conclusions.
References.

7 Self-supported Asymmetric Catalysts (Wenbin Lin and David J. Mihalcik).
7.1 Introduction.
7.2 Self-supported Asymmetric Catalysts Formed by Linking Catalytically Active Subunits via Metal–Ligand Coordination.
7.3 Self-supported Asymmetric Catalysts Formed by Post-synthetic Modifications of Coordination Polymers.
7.4 Self-supported Asymmetric Catalysts Formed by Linking Multitopic Chiral Ligands with Catalytic Metal Centers.
7.5 Conclusions and Outlook.
Acknowledgments.
References.

8 Fluorous Chiral Catalyst Immobilization (Tibor Sos).
8.1 Introduction.
8.2 Fluorous Chemistry and its Basic Recovery Concepts.
8.3 Application of Fluorous Chiral Catalysts.
8.4 Summary.
References.

9 Biphasic Catalysis: Catalysis in Supercritical CO2 and in Water (Simon L. Desset and David J. Cole-Hamilton).
9.1 Introduction.
9.2 Biphasic Catalysis.
9.3 Aqueous Biphasic Catalysis.
9.4 Supercritical Carbon Dioxide.
9.5 Conclusion.
References.

10 Asymmetric Catalysis in Ionic Liquids (Lijin Xu and Jianliang Xiao).
10.1 Introduction.
10.2 Metal-catalyzed Asymmetric Reactions in ILs.
10.3 Asymmetric Organocatalytic Reactions in ILs.
10.4 Concluding Remarks.
References.

11 Recoverable Organic Catalysts (Maurizio Benaglia).
11.1 Introduction.
11.2 Achiral Organic Catalysts.
11.3 Chiral Organic Catalysts.
11.4 Catalysts Derived from Amino Acids.
11.5 General Considerations on Recyclable Organocatalysts.
11.6 Outlook and Perspectives.
References.

12 Organic Polymer-microencapsulated Metal Catalysts (Jun Ou and Patrick H. Toy).
12.1 Introduction.
12.2 Non-cross-linked Polymer-microencapsulated Catalysts.
12.3 Cross-linked Polymer-microencapsulated Catalysts.
12.4 Summary Table.
12.5 Conclusions.
References.

13 Organic Synthesis with Mini Flow Reactors Using Immobilised Catalysts (Sascha Ceylan and Andreas Kirschning).
13.1 Introduction.
13.2 Catalysis in Mini Flow Reactors with Immobilised Catalysts.
13.3 Miscellaneous Enabling Techniques for Mini Flow Systems.
13.4 Perspectives and Outlook.
References.
14 Homogeneous Catalysis Using Microreactor Technology (Johan C. Brandt and Thomas Wirth).
14.1 Introduction.
14.2 Acid-catalysed Reactions.
14.3 Liquid–liquid Biphasic Systems.
14.4 Photocatalysis.
14.5 Asymmetric Catalytic Reactions.
14.6 Unusual Reaction Conditions.
References.

15 Catalyst Immobilization Strategy: Some General Considerations and a Comparison of the Main Features of Different Supports (Franco Cozzi).
15.1 Introduction.
15.2 General Considerations on Catalyst Immobilization.
15.3 Comparison of Different Supports Employed for the Immobilization of Proline.
15.4 Comparison of Different Supports Employed for the Immobilization of Bis(oxazolines).
15.5 Conclusions.
References.
Index.