The Molecular Mechanism of Enzymatic Glycosyl Transfer with Retention of Configuration: Evidence for a Short-Lived Oxocarbenium-Like Species

被引：84

作者：

Ardevol, Albert ^{[1
]}

Rovira, Carme ^{[1
,2
]}

机构：

[1] Parc Cient Barcelona, Comp Simulat & Modeling Lab CoSMoLAB, Barcelona 08028, Spain

[2] ICREA, Barcelona 08020, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 46期

关键词：

computational chemistry; glycosides; reaction mechanisms; transferases; transition states; RETAINING GALACTOSYLTRANSFERASE LGTC; DYNAMICS SIMULATIONS; QM/MM METADYNAMICS; GLYCOSYLTRANSFERASES; HYDROLYSIS; INSIGHT; COMPLEX;

D O I：

10.1002/anie.201104623

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A quantum leap: By means of quantum mechanics/molecular mechanics metadynamics simulations, a front-face SNi-type reaction for glycosyl transfer with retention of the anomeric configuration is shown to be feasible. A short-lived oxocarbenium-like species (see picture; O red, P gold, N blue, C black) is identified and provides the complete itinerary of this long sought after molecular mechanism. © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：10897 / 10901

页数：5

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