In the presence of a catalytic amount of an imidodiphosphoric acid, enantioselective desymmetrization of bicyclic bislactones by reaction with alcohols took place smoothly to afford enantiomerically enriched mono acids having an all-carbon stereogenic center. Concise catalytic enantioselective syntheses of both (-)-rhazinilam and (-)-leucomidine B were subsequently developed using (S)-methyl 4-ethyl-4-formylpimelate monoacid as a common starting material.