Asymmetric three-component olefin dicarbofunctionalization enabled by photoredox and copper dual catalysis

The intermolecular three-component alkene vicinal dicarbofunctionalization (DCF) reaction allows installation of two different carbon fragments. Despite extensive investigation into its ionic chemistry, the enantioseletive radical-mediated versions of DCF reactions remain largely unexplored. Herein, we report an intermolecular, enantioselective three-component radical vicinal dicarbofunctionalization reaction of olefins enabled by merger of radical addition and cross-coupling using photoredox and copper dual catalysis. Key to the success of this protocol relies on chemoselective addition of acyl and cyanoalkyl radicals, generated in situ from the redox-active oxime esters by a photocatalytic N-centered iminyl radical-triggered C-C bond cleavage event, onto the alkenes to form new carbon radicals. Single electron metalation of such newly formed carbon radicals to TMSCN-derived L1Cu(II)(CN)(2) complex leads to asymmetric cross-coupling. This three-component process proceeds under mild conditions, and tolerates a diverse range of functionalities and synthetic handles, leading to valuable optically active beta -cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (>60 examples, up to 97% ee). Vicinal dicarbofunctionalization (DCF) reactions of alkenes have been extensively explored in ionic chemistry but the enantioselective radical mediated version of DCF remains largely unexplored. Here, the authors demonstrate a radical vicinal DCF reaction of olefins by merging of radical addition and cross-coupling using photoredox and copper dual catalysis.

Automated summary

The radical vicinal dicarbofunctionalization (DCF) reaction of olefins by merging of radical addition and cross-coupling using photoredox and copper dual catalysis demonstrates high enantioselectivity and tolerance towards a wide range of functionalities. This protocol provides a valuable synthetic tool for the construction of optically active compounds with potential applications in organic synthesis.