Enhancing the Tsuji-Trost Reaction via 1,3-Diene Formation.

-metal center, the proposed 1,3-diene-formation principle enables diverse allyl electrophiles to react with different types of carbon and phosphine nucleophiles with good enantioconvergence efficiency. In addition, the stereoselective migration of the whole allyl unit is established through deracemization, which differs from prior metal walking models that are limited to alkene migration. Convergent synthesis and concise preparations of a couple of natural products highlight the practical value of the method. Mechanistic studies support 1,3-diene formation as the key process for deracemization and that the final allylic substitution is a slow and rate-determining step.