Rhodium-Catalyzed Enantioselective Desymmetrization

Significance

A rhodium-catalyzed enantioselective desymmetrization of various glutaric anhydrides with carbon nucleophiles generates syn-deoxypolypropionate synthons in good yields and high ee values. The nucleophiles are commercially available or in situ generated alkyl or benzyl zinc reagents; aryl nucleophiles, however, are not compatible. A good range of alkyl nucleophiles, including those with an ester or chloride moiety, is shown. Electron-rich benzylic nucleophiles result in lower ee values due to a background reaction. Some examples of post-modifications of the product are also provided, including a deoxygenation and a dia­stereoselective reduction producing an intermediate to the synthesis of a beetle pheromone.