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Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage
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Cullen, William, Misuraca, M. Cristina, Hunter, Christopher A., Williams, Nicholas H. and Ward, Michael D. (2016) Highly efficient catalysis of the Kemp elimination in the cavity of a cubic coordination cage. Nature Chemistry, 8 (3). pp. 231-236. doi:10.1038/nchem.2452 ISSN 1755-4330.
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Official URL: http://dx.doi.org/10.1038/nchem.2452
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 × 105, 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.
Item Type: | Journal Article | ||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
Journal or Publication Title: | Nature Chemistry | ||||||
Publisher: | Nature Publishing Group | ||||||
ISSN: | 1755-4330 | ||||||
Official Date: | 15 February 2016 | ||||||
Dates: |
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Volume: | 8 | ||||||
Number: | 3 | ||||||
Page Range: | pp. 231-236 | ||||||
DOI: | 10.1038/nchem.2452 | ||||||
Status: | Peer Reviewed | ||||||
Publication Status: | Published | ||||||
Access rights to Published version: | Restricted or Subscription Access |
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