Three-Component Olefin Dicarbofunctionalization Enabled by Nickel/Photoredox Dual Catalysis

An intermolecular, photocatalytic dicarbofunctionalization
(DCF)
of olefins enabled by the merger of Giese-type addition with Ni/photoredox
dual catalysis has been realized. Capitalizing on the rapid addition
of 3° radicals to alkenes and their reluctance toward single
electron metalation to Ni complexes, regioselective alkylation and
arylation of olefins is possible. This dual catalytic method not only
permits elaborate species to be assembled from commodity materials,
but also allows quaternary and tertiary centers to be installed in
a singular, chemoselective olefin difunctionalization. This multicomponent
process occurs under exceptionally mild conditions, compatible with
a diverse range of functional groups and synthetic handles such as
pinacolboronate esters. This technology was directly applied to the
synthesis of an intermediate to a preclinical candidate (TK-666) and
its derivatives.