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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 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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Organic & Biomolecular Chemistry
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