Asymmetric Three-Component Olefin Dicarbofunctionalization Enabled by Photoredox and Copper Dual Catalysis

14 December 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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 is presented here. 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 β–cyano ketones and alkyldinitriles, respectively, in a highly enantioselective manner (> 60 examples, up to 97% ee).


photoredox catalysis
copper catalysis
iminyl radicals
chiral nitriles
asymmetric multicomponent radical reaction

Supplementary materials

Supporting Information-20201129-final


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