Starting from (R)-epichlorohydrin led to (S)-glycidyl pivalate samples with [α]D values of 18.8 ° and 18.9 °. Attack of the pivalate anion on the epoxide rather than the primary chloride rationalizes this observation. Despite these highly encouraging results, analysis of the recovered epichlorohydrin revealed that the epoxide racemized over the course of the reaction.