Abstract: | The enantioselective desymmetrization of cyclic meso‐anhydrides with benzyl trifluoroborates under nickel‐photoredox catalysis is described. The reaction tolerates a variety of sterically and electronically different trifluoroborates, as well as structurally unique cyclic anhydrides. The trans isomer of the keto‐acid products is also observed at varying levels dependent on the trifluoroborate identity and relative catalyst loading. A mechanism involving decarbonylation and Ni?C bond homolysis of a NiII adduct is proposed. This feature allows access to a trans keto‐acid as the major product in high enantioselectivity from a cis meso anhydride. |