Abstract 25-Hydroxyvitamin D 2 as synthesized conveniently and stereoselectively for the first time by utilizing Sharpless' chiral epoxidation and the subsequent regio-and stereoselective methylation with lithium dimethylcuprate to introduce the desired chirality at C (24) and the reductive elimination of the vicinal hydroxy sulfone to introduce stereoselectively the E double bond at C (22) of the target molecule.