Issue 22, 2023

Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes

Abstract

A photocatalytic C–H gem-difunctionalization of 1,3-benzodioxoles with two different alkenes for the synthesis of highly functionalized monofluorocyclohexenes is described. Using 4CzIPN as the photocatalyst, the direct single electron oxidation of 1,3-benzodioxoles allows their defluorinative coupling with α-trifluoromethyl alkenes to produce gem-difluoroalkenes in a redox-neutral radical polar crossover manifold. The C–H bond of the resultant γ,γ-difluoroallylated 1,3-benzodioxoles was further functionalized via radical addition to electron-deficient alkenes using a more oxidizing iridium photocatalyst. The capture of in situ generated carbanions by an electrophilic gem-difluoromethylene carbon and consecutive β-fluoride elimination afford monofluorocyclohexenes. The synergistic combination of multiple termination pathways of carbanions enables rapid incorporation of molecular complexity via stitching simple and readily accessible starting materials together.

Graphical abstract: Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes

Supplementary files

Article information

Article type
Edge Article
Submitted
17 feb. 2023
Accepted
10 maí 2023
First published
12 maí 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 6045-6051

Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes

J. Tian and L. Zhou, Chem. Sci., 2023, 14, 6045 DOI: 10.1039/D3SC00912B

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