Open AccessThree-Component Olefin Dicarbofunctionalization Enabled by Nickel/Photoredox Dual Catalysis
Author(s) -
Mark W. Campbell,
Jordan S. Compton,
Christopher B. Kelly,
Gary A. Molander
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b08282
Subject(s) - chemistry , regioselectivity , olefin fiber , alkylation , catalysis , photoredox catalysis , combinatorial chemistry , metalation , radical , nickel , intermolecular force , dual role , photocatalysis , photochemistry , organic chemistry , molecule
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.