A novel synthetic strategy toward the asymmetric synthesis of vicinal diols bearing a tertiary center is presented. The method encompasses the dinuclear Mg-catalyzed asymmetric addition of ethyl diazoacetate into several aldehydes, oxidation of the diazo functionality, and diastereoselective alkyl transfer of various organometallics into the resulting chiral beta-hydroxy-alpha-ketoesters to afford a diverse range of 1,2-diols in high yield, diastereoselectivity, and chirality transfer.