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

ABSTRACT: 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.

SUBMITTER: Campbell MW

PROVIDER: S-EPMC7086343 | biostudies-literature | 2019 Dec

REPOSITORIES: biostudies-literature

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

Campbell Mark W MW Compton Jordan S JS Kelly Christopher B CB Molander Gary A GA

Journal of the American Chemical Society 20191213 51

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 quaternar ...[more]

PMID: 31833357

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