Work

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

Year: 2019

Type: article

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.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.9b08282

Authors: Mark W. Campbell, Jordan S. Compton, Christopher B. Kelly, Gary A. Molander

Institutions: University of Pennsylvania, Virginia Commonwealth University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, Virginia Commonwealth University, National Institute of General Medical Sciences

Award: Accessing New Chemical Space via Organic Synthesis