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Abstract
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).
Supplementary materials
Title
Supporting Information-20201129-final
Description
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