Kinetics and mechanisms of reactions of thiol, thiono and dithio analogues of carboxylic esters with nucleophiles. An update

Abstract

The objective of this review is to update a previous one (published in 1999) on the kinetics and mechanism of the reactions of thioesters, thiocarbonates and analogous thiocarbonyl derivatives with different nucleophiles in solution. There has been abundant literature on this topic since 1999 and it is of interest to chemists and biochemists to have a comprehensive view on the recent developments on the title reactions. Most of these occur through a tetrahedral intermediate, usually in steady state condition, whose breakdown generally leads to the final products (stepwise reactions). Nevertheless, depending on the stability of the tetrahedral intermediate, some reactions take place in one step (concerted mechanism). This review also discusses the factors that affect the stability of this intermediate, which in turn determines the pathway followed by the reaction.