A mechanistic study of sialic acid mutarotation: Implications for mutarotase enzymes

被引：8

作者：

Chan, Jefferson ^{[1
]}

Sandhu, Gurtej ^{[1
]}

Bennet, Andrew J. ^{[1
]}

机构：

[1] Simon Fraser Univ, Dept Chem, Burnaby, BC V5A 1S6, Canada

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2011年 / 9卷 / 13期

关键词：

NMR-SPECTROSCOPY; DEUTERIUM OXIDE; NEURAMINIC ACID; CATALYSIS; GLUCOSE; H-1;

D O I：

10.1039/c1ob05079f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mutarotation of N-acetylneuraminic acid (Neu5Ac) proceeds by four kinetically distinct pathways: (i) the acid-catalyzed reaction of neutral Neu5Ac; (ii) the spontaneous reaction of the carboxylic acid (the kinetically equivalent acid-catalyzed reaction on the anion being ruled out by the solvent deuterium kinetic isotope effect of 3.74 +/- 0.68); (iii) a spontaneous, water-catalyzed, reaction of the anion; and (iv) a specific-base catalyzed reaction of the anion. The magnitude of the solvent kinetic isotope effect, k(H2O)/k(D2O) = 4.48 +/- 0.74 is consistent with a ring-opening transition state in which a water molecule is deprotonating the anomeric hydroxyl group in concert with strengthening solvation of the ring oxygen atom. The mechanistic implications for Neu5Ac mutarotases are discussed.

引用

页码：4818 / 4822

页数：5

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