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. 2021 Jan 4;60(1):186-190.
doi: 10.1002/anie.202010839. Epub 2020 Oct 29.

Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center

Zexian Li  1 , Minyan Wang  1 , Zhuangzhi Shi  1
Affiliations

Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center

Zexian Li et al. Angew Chem Int Ed Engl. .

Abstract

An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy)3 , visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.

Keywords: fluorine; olefins; photochemistry; radicals; rearrangement.

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