The preparation of methyl-substituted synthons of high enantiomerical purities by Claisen transposition, cuprate substitution of secondary optically active alcohols and microbial reduction of β-ketoesters was investigated and applied to the synthesis of (2S, 3S, 7S) and (2S, 3R, 7R)-3, 7-dimethylpentadecan-2-ol, the pheromones of diprionid species of pine sawflies.