Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters

被引：15

作者：

Babtie, Ann C. ^{[2
]}

Lima, Marcelo F. ^{[1
,2
]}

Kirby, Anthony J. ^{[1
]}

Hollfelder, Florian ^{[2
]}

机构：

[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

[2] Univ Cambridge, Dept Biochem, Cambridge CB2 1GA, England

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2012年 / 10卷 / 40期

基金：

英国工程与自然科学研究理事会; 英国生物技术与生命科学研究理事会;

关键词：

ALKALINE-PHOSPHATASE SUPERFAMILY; P-NITROPHENYL PHOSPHATE; SINGLE TRANSITION-STATE; CATALYTIC PROMISCUITY; SULFATE ESTERS; REACTIVITY; MECHANISM; NUCLEOPHILES; INHIBITION; METABOLISM;

D O I：

10.1039/c2ob25699a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The hydrolytic reactions of sulfonate esters have previously been considered to occur by concerted mechanisms. We now report the observation of a break in a Bronsted correlation for the alkaline hydrolysis of aryl benzenesulfonates. On either side of a break-point, beta(leaving) group values of -0.27 (pK(a) < 8.5) and -0.97 (pK(a) > 8.5) are measured. These data are consistent with a two-step mechanism involving a pentavalent intermediate that is also supported by QM/MM calculations. The emerging scenario can be explained by the combined effect of a strong nucleophile with a poor leaving group that compel a usually concerted reaction to favour a stepwise process.

引用

页码：8095 / 8101

页数：7

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