The reactivity of phosphate esters. Reactions of diesters with nucleophiles
Abstract
The reactions of a wide range of nucleophiles with a series of aryl methyl phosphate ester anions involve concerted nucleophilic displacement at phosphorus. The attack of neutral nucleophiles is slower than the corresponding reactions of both triesters and monoester monoanions. SN2(P) reactions involving the attack of anions on phosphate diester anions are observed, and are shown to be retarded by a factor of ca. 100 times in rate, which is ascribed to an adverse electrostatic effect. Sensitivities to both nucleophile and leaving group are considerable, and show some dependence on reactivity: they are also apparently affected by the electrostatic effect.