Physical Organic Perspectives on Phospho Group Transfer From Phosphates and Phosphinates

Abstract

As phosphoryl transfer reactions are ubiquitous in biological chemistry, organic chemists have been very interested in the mechanisms of phosphate and phosphinate esters. Physical organic chemistry methods, including stereochemical studies, linear free energy relationships, and, most recently, heavy-atom kinetic isotope effects, have been used in the quest for mechanistic information about the chemistry of these compounds. This review summarizes what has been learned about the uncatalyzed phosphoryl transfer reactions of phosphate and phosphinate esters. Keywords: dianions, hydrolysis, phosphorothioate analogs, isotope, solvolysis