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Co-immobilization of an Enzyme and a Metal into the Compartments of Mesoporous Silica for Cooperative Tandem Catalysis: An Artificial Metalloenzyme
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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2013 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 52, no 52, 14006-14010 p.Article in journal (Refereed) Published
Abstract [en]

Surpassing nature: A hybrid catalyst in which Candida antarctica lipase B and a nanopalladium species are co-immobilized into the compartments of mesoporous silica is presented. The metal nanoparticles and the enzyme are in close proximity to one another in the cavities of the support. The catalyst mimics a metalloenzyme and was used for dynamic kinetic resolution of a primary amine in high yield and excellent enantioselectivity.

Place, publisher, year, edition, pages
2013. Vol. 52, no 52, 14006-14010 p.
Keyword [en]
artificial deracemase, biocatalysis, dynamic kinetic resolution, hybrid catalysts, metal catalysis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-96701DOI: 10.1002/anie.201306487ISI: 000328531100019OAI: oai:DiVA.org:su-96701DiVA: diva2:667174
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount: 7;

Available from: 2013-11-25 Created: 2013-11-25 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Transition Metal-Catalyzed Redox Reactions: A Journey from Homogeneous Ruthenium to Heterogeneous Palladium Catalysis
Open this publication in new window or tab >>Transition Metal-Catalyzed Redox Reactions: A Journey from Homogeneous Ruthenium to Heterogeneous Palladium Catalysis
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The first part of the thesis covers the development and utilization of electronically modified (pentaarylcyclopentadienyl)Ru-complexes in the racemization of secondary alcohols. This study revealed that the electronic properties of the substrate were the main factors dictating whether β-hydride elimination or hydride re-addition becomes the rate-determining step of the racemization process. With this knowledge in hand, it proved to be possible to design more efficient racemization protocols by matching the electronic properties of catalyst and substrate.

The second part describes mechanistic work that aimed at elucidating the role of CO dissociation in the mechanism of secondary alcohol racemization catalyzed by a (pentaarylcyclopentadienyl)Ru-complex. From CO exchange studies, we demonstrated that CO dissociation occurred in the catalytically active tert-BuO-species as well as in the chloride precatalyst. Furthermore, an inhibition study showed that an increase of the partial pressure of CO had a negative influence on the racemization rate. Together, these two observations provide strong support for CO dissociation as a key step in the racemization of secondary alcohols.

The third part concerns the improved synthesis and characterization of a heterogeneous catalyst consisting of Pd nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam. The developed Pd nanocatalyst was found to be a highly efficient and recyclable catalyst for the aerobic oxidation of a wide range of primary and secondary alcohols to the corresponding aldehydes and ketones.

The fourth part deals with the successful application of the Pd nanocatalyst in chemically-induced H2O oxidation, when using either ceric ammonium nitrate or [Ru(bpy)3]3+ as the terminal oxidant. Remarkably, the Pd nanocatalyst proved to catalyze this reaction with high efficiency and the measured TOF was found to greatly exceed those of current state-of-the-art metal oxide catalysts.

The fifth and final part describes the co-immobilization of Pd nanoparticles and the enzyme Candida Antarctica Lipase B into the same cavities of mesocellular foam, to generate a “metalloenzyme-like” hybrid catalyst for the dynamic kinetic resolution of a primary amine. The close proximity of the two catalytic species led to an enhanced cooperativity between them and resulted in an overall more efficient tandem process. 

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2013. 95 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-96713 (URN)978-91-7447-828-0 (ISBN)
Public defence
2014-01-24, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 5: Epub ahead of print.

Available from: 2014-01-02 Created: 2013-11-26 Last updated: 2014-06-12Bibliographically approved

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