Cullen, W., Misuraca, M.C., Hunter, C.A. et al. (2 more authors) (2016) Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage. Nature Chemistry, 8 (3). pp. 231-236. ISSN 1755-4330
Abstract
The hollow cavities of coordination cages can provide an environment for enzyme-like catalytic reactions of small-molecule guests. Here, we report a new example (catalysis of the Kemp elimination reaction of benzisoxazole with hydroxide to form 2-cyanophenolate) in the cavity of a water-soluble M8L12 coordination cage, with two features of particular interest. First, the rate enhancement is among the largest observed to date: at pD 8.5, the value of kcat/kuncat is 2 × 10(5), due to the accumulation of a high concentration of partially desolvated hydroxide ions around the bound guest arising from ion-pairing with the 16+ cage. Second, the catalysis is based on two orthogonal interactions: (1) hydrophobic binding of benzisoxazole in the cavity and (2) polar binding of hydroxide ions to sites on the cage surface, both of which were established by competition experiments.
Metadata
Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 The Authors. Reproduced in accordance with the publisher's self-archiving policy. |
Keywords: | Homogeneous catalysis; Molecular capsules |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 03 Mar 2016 10:53 |
Last Modified: | 05 Nov 2017 14:11 |
Published Version: | https://dx.doi.org/10.1038/nchem.2452 |
Status: | Published |
Publisher: | Nature Publishing Group |
Identification Number: | https://doi.org/10.1038/nchem.2452 |
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