Stereospecific control of the citrate synthase mediated synthesis of (2R,3R)-3-fluorocitrate by the relative stabilities of the intermediate fluoroenolates

Abstract

A model for the stereochemical course of enzymatically mediated condensations involving fluoroacetyl–CoA is provided by ab initio calculations of the relative stabilities of the E- and Z-isomers of fluorothioacyl enols and enolates, in which we suggest the enolate intermediate is substantially protonated for citrate synthase but not for malate synthase.