Intramolecular general acid catalysis of sulfate transfer — Nucleophilic attack by oxyanions on the SO3– group

Kirby, Anthony J.; Gesser, José Carlos; Hollfelder, Florian; Priebe, Jacks P.; Nome, Faruk
September 2005
Canadian Journal of Chemistry;Sep2005, Vol. 83 Issue 9, p1629
Academic Journal
The mechanism of hydrolysis of 8-N,N-dimethylaminonaphthyl sulfate closely resembles that of the corresponding phosphate monoester. Nucleophilic attack by water on the sulfate group of the zwitterion is catalyzed by the neighbouring dimethylammonium group, acting as a particularly efficient general acid through the intramolecular hydrogen bond. This hydrogen bond is present in both reactant and product, but is strongest in the transition state. Transfer of the sulfuryl group to oxygen nucleophiles, including water and carboxylate anions, shows steric and electrostatic effects, and a sensitivity to basicity which is low, but significantly higher than expected for uncatalyzed transfer of the SO3– group.


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