Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters?
Organic & Biomolecular Chemistry Pub Date: 2012-07-26 DOI: 10.1039/C2OB25699A
Abstract
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 Br?nsted correlation for the alkaline hydrolysis of aryl benzenesulfonates. On either side of a break-point, βleaving group values of ?0.27 (pKa < 8.5) and ?0.97 (pKa > 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.
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Journal Name：Organic & Biomolecular Chemistry
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CAS no.: 89640-58-4
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