Oxygen functionalized chiral alkoxymethylketone, derived from (2R, 4R)-2, 4-pentanediol, provided an efficient chiral environment in the reaction with organometallics which resulted in the either stereoselection depending on metal used; ie, the reactions with MeLi and MeTi (O i Pr) 3 selectively furnished the corresponding (S)-and (R)-tertiary alcohols, respectively.