Unambiguous evidence for efficient chemical catalysis of adenosine ester aminolysis by its 2′/3′-OH

被引：21

作者：

Bayryamov, Stanislav G. ^{[1
]}

Rangelov, Miroslav A. ^{[1
]}

Mladjova, Aneta P. ^{[1
]}

Yomtova, Vihra ^{[1
]}

Petkov, Dimiter D. ^{[1
]}

机构：

[1] Bulgarian Acad Sci, Inst Organ Chem, Lab BioCatalysis, BU-1113 Sofia, Bulgaria

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 18期

关键词：

D O I：

10.1021/ja068447g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Intramolecular aminolysis reactions, catalyzed by a vicinal OH group, were studied computationally as model reactions of ribosome-catalyzed intracomplex aminolysis. The results predicts 2-6-fold higher enthalpic than entropic contribution to the reduction of the activation free energy, caused by the combined proximity effect of the attacking syn-NH2 group and the catalytic syn-OH group. The acceleration predicted by the theory is supported by the observed instantaneous lactamization of ornithinyl adenosine as compared to the much slower lactamization of ornithinyl 2'-deoxyadenosine. This observation is the first unambiguous experimental demonstration of chemical catalysis of the 1,2-diol monoester aminolysis by its vicinal 2-OH groupthe reaction naturally catalyzed by ribosome.

引用

页码：5790 / +

页数：3

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