Asymmetric radical allylation of β-keto esters with vinyl cyclopropanes by dual photoredox/nickel catalysis

Radical-involved allylation reactions have emerged as a powerful platform for construction of carbon-carbon and carbonheteroatom bonds, facilitating the strategic incorporation of diverse allyl moieties. Nevertheless, this burgeoning field still faces ongoing challenges, including limitations of radical precursors and coupling partners, and difficulties in achieving enantiocontrol. Herein, we report for the first time a highly enantioselective radical allylation involving beta-keto esters with vinyl cyclopropanes utilizing a synergistic dual photoredox/nickel catalysis under visible light irradiation. The mild and redox-neutral catalytic protocol demonstrates an extensive substrate compatibility and good functional tolerance, providing access to enantioenriched beta-keto esters featuring quaternary alpha-stereocenter with good yields and high enantioselectivities. Preliminary mechanistic studies have uncovered that the success of the reaction hinges on the dual roles of nickel catalyst, including in situ formation of photoredox sensitive substrate/Ni complex and the ensuing asymmetric radical addition step.