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Bi-Catalyzed Trifluoromethylation of C(sp²)-H Bonds under Light.

ABSTRACT: We disclose a Bi-catalyzed C-H trifluoromethylation of (hetero)arenes using CF₃SO₂Cl under light irradiation. The catalytic method permits the direct functionalization of various heterocycles bearing distinct functional groups. The structural and computational studies suggest that the process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for a main group element. The catalytic cycle starts with rapid oxidative addition of CF₃SO₂Cl to a low-valent Bi(I) catalyst, followed by a light-induced homolysis of Bi(III)-O bond to generate a trifluoromethyl radical upon extrusion of SO₂, and is closed with a hydrogen-atom transfer to a Bi(II) radical intermediate.

SUBMITTER: Tsuruta T

PROVIDER: S-EPMC10690797 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature

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Bi-Catalyzed Trifluoromethylation of C(sp2)-H Bonds under Light.

Tsuruta Takuya T Spinnato Davide D Moon Hye Won HW Leutzsch Markus M Cornella Josep J

Journal of the American Chemical Society 20231114 47

We disclose a Bi-catalyzed C-H trifluoromethylation of (hetero)arenes using CF3SO2Cl under light irradiation. The catalytic method permits the direct functionalization of various heterocycles bearing distinct functional groups. The structural and computational studies suggest that the process occurs through an open-shell redox manifold at bismuth, comprising three unusual elementary steps for a main group element. The catalytic cycle starts with rapid oxidative addition of ...[more]

PMID: 37963280

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