On the origins of enhanced reactivity of five-membered cyclic phosphate esters. The relative contributions of enthalpic and entropic factors

R Kluger, SD Taylor

Index: Kluger, Ronald; Taylor, Scott D. Journal of the American Chemical Society, 1990 , vol. 112, # 18 p. 6669 - 6671

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Citation Number: 52

Abstract

Abstract: The hydrolysis of five-membered cyclic phosphate and phosphonate esters is about 106-fold more rapid than the hydrolysis of related acyclic esters. The origin of the enhanced reactivity of the cyclic esters has been ascribed to enthalpic factors, associated with ground-state strain, and to entropic factors, associated with optimal orbital orientations. The temperature dependence of the rates of alkaline hydrolysis of ethyl and methyl esters ...