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
Item Type: | Article |
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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: | 10.1038/nchem.2452 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:95939 |