A rhodium phosphinooxazoline system allows for an efficient enantioselective desymmetrization of dimethyl glutaric anhydride. Both commercially available and in situ generated sp(3)-organozinc nucleophiles couple efficiently in high enantiomeric excess. This chemistry has also been extended to other 3,5-disubstituted anhydrides, and further elaboration has enabled the synthesis of potentially useful syn-deoxypolypropionate fragments.