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Hong, Sung You
Synthetic Organic Chemistry Laboratory
Research Interests
  • Synthetic organic chemistry, transition metals, oxidation state

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Mechanistic evidence for a front-side, S(N)i-type reaction in a retaining glycosyltransferase

Cited 47 times inthomson ciCited 41 times inthomson ci
Title
Mechanistic evidence for a front-side, S(N)i-type reaction in a retaining glycosyltransferase
Author
Lee, Seung SeoHong, Sung YouErrey, James C.Izumi, AtsushiDavies, Gideon J.Davis, Benjamin G.
Issue Date
2011-09
Publisher
NATURE PUBLISHING GROUP
Citation
NATURE CHEMICAL BIOLOGY, v.7, no.9, pp.631 - 638
Abstract
A previously determined crystal structure of the ternary complex of trehalose-6-phosphate synthase identified a putative transition state-like arrangement based on validoxylamine A 6'-O-phosphate and uridine diphosphate in the active site. Here linear free energy relationships confirm that these inhibitors are synergistic transition state mimics, supporting front-face nucleophilic attack involving hydrogen bonding between leaving group and nucleophile. Kinetic isotope effects indicate a highly dissociative oxocarbenium ion-like transition state. Leaving group O-18 effects identified isotopically sensitive bond cleavages and support the existence of a hydrogen bond between the nucleophile and departing group. Bronsted analysis of nucleophiles and Taft analysis highlight participation of the nucleophile in the transition state, also consistent with a front-face mechanism. Together, these comprehensive, quantitative data substantiate this unusual enzymatic reaction mechanism. Its discovery should prompt useful reassessment of many biocatalysts and their substrates and inhibitors.
URI
https://scholarworks.unist.ac.kr/handle/201301/3821
URL
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=84860389788
DOI
10.1038/NCHEMBIO.628
ISSN
1552-4450
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CHM_Journal Papers
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