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

…, MF Lima, AJ Kirby, F Hollfelder

Index: Babtie, Ann C.; Lima, Marcelo F.; Hollfelder, Florian; Kirby, Anthony J. Organic and Biomolecular Chemistry, 2012 , vol. 10, # 40 p. 8095 - 8101,7

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Citation Number: 12

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 Brønsted 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 ...