The reaction of the α-carbanion of p-tolyl 2-(trimethylsilyl)ethyl sulfoxide with esters followed by reductionwith DIBAL gave α-(trimethylsilyl)methyl-β-hydroxysulfoxides with high stereoselectivity. The stereoselective reactionwas demonstrated to proceed through a dynamic kineticresolution pathway via a six-membered cyclic transitionstate involving Si−O interaction. These reactions provide aconvenient route for the synthesis of optically pure allylicalcohols.