Highly efficient, direct, and enantioselective synthesis of useful chiral building blocks with excellent ee was performed by the catalytic asymmetric acylation of ineso-1,3-propanediols. A structurally most simple meso-1,3-propanediol, 2-methyl-1,3-propanediol, was asymmetrized in 96% ee catalyzed by 0.5 mol% of chiral 1,2-diamine.