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Catalysts 2018, 8(2), 51; doi:10.3390/catal8020051

An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins

Department of Chemistry, University of California, Riverside, CA 92521, USA
Department of Chemical & Environmental Engineering and Materials Science & Engineering Program, University of California, Riverside, CA 92521, USA
Illinois Rocstar LLC, P.O. Box 3001, Champaign, IL 61826, USA
Authors to whom correspondence should be addressed.
Received: 30 September 2017 / Revised: 25 January 2018 / Accepted: 25 January 2018 / Published: 29 January 2018
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We performed a computational investigation of the mechanism by which cyclodextrins (CDs) catalyze Diels-Alder reactions between 9-anthracenemethanol and N-cyclohexylmaleimide. Hydrogen bonds (Hbonds) between N-cyclohexylmaleimide and the hydroxyl groups of cyclodextrins were suggested to play an important role in this catalytic process. However, our free energy calculations and molecular dynamics simulations showed that these Hbonds are not stable, and quantum mechanical calculations suggested that the reaction is not promoted by these Hbonds. The binding of 9-anthracenemethanol and N-cyclohexylmaleimide to cyclodextrins was the key to the catalytic process. Cyclodextrins act as a container to hold the two reactants in the cavity, pre-organize them for the reactions, and thus reduce the entropy penalty to the activation free energy. Dimethyl-β-CD was a better catalyst for this specific reaction than β-CD because of its stronger van der Waals interaction with the pre-organized reactants and its better performance in reducing the activation energy. This computational work sheds light on the mechanism of the catalytic reaction by cyclodextrins and introduces new perspectives of supramolecular catalysis. View Full-Text
Keywords: flexibility; preorganization; host-guest; nonpolar pocket; design and synthesis; enzyme flexibility; preorganization; host-guest; nonpolar pocket; design and synthesis; enzyme

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Chen, W.; Sun, L.; Tang, Z.; Ali, Z.A.; Wong, B.M.; Chang, C.-E.A. An MM and QM Study of Biomimetic Catalysis of Diels-Alder Reactions Using Cyclodextrins. Catalysts 2018, 8, 51.

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