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. 2017 Nov 20;56(47):15073-15077.
doi: 10.1002/anie.201709487. Epub 2017 Oct 24.

Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics

Simon B Lang  1 , Rebecca J Wiles  1 , Christopher B Kelly  1 , Gary A Molander  1
Affiliations

Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics

Simon B Lang et al. Angew Chem Int Ed Engl. .

Abstract

Described is a facile, scalable route to access functional-group-rich gem-difluoroalkenes. Using visible-light-activated catalysts in conjunction with an arsenal of carbon-radical precursors, an array of trifluoromethyl-substituted alkenes undergoes radical defluorinative alkylation. Nonstabilized primary, secondary, and tertiary radicals can be used to install functional groups in a convergent manner, which would otherwise be challenging by two-electron pathways. The process readily extends to other perfluoroalkyl-substituted alkenes. In addition, we report the development of an organotrifluoroborate reagent to expedite the synthesis of the requisite trifluoromethyl-substituted alkene starting materials.

Keywords: alkenes; alkylation; fluorine; photochemistry; radicals.

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Figures

Figure 1
Figure 1
Representative applications of gem-difluoroalkenes.
Figure 2
Figure 2
Scale-up of defluorinative alkylation with subsequent cross-coupling.
Figure 3
Figure 3
Development and implementation of an organotrifluoroborate for trifluoromethyl-substituted styrene synthesis.
Scheme 1
Scheme 1
Typical routes to gem-difluoroalkenes.
Scheme 2
Scheme 2
A convergent route to gem-difluoroalkenes via radical alkylation.
See this image and copyright information in PMC

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