Radical Trifluoroacetylation of Alkenes Triggered by a Visible-Light-Promoted C-O Bond Fragmentation of Trifluoroacetic Anhydride
- Journal Article
Rights / licenseCreative Commons Attribution-NonCommercial 4.0 International
We report a mild and operationally simple trifluoroacylation strategy of olefines, that utilizes trifluoroacetic anhydride as a low-cost and readily available reagent. This light-mediated process is fundamentally different from conventional methodologies and occurs through a trifluoroacyl radical mechanism promoted by a photocatalyst, which triggers a C-O bond fragmentation. Mechanistic studies (kinetic isotope effects, spectroelectrochemistry, optical spectroscopy, theoretical investigations) highlight the evidence of a fleeting CF3CO radical under photoredox conditions. The trifluoroacyl radical can be stabilized under CO atmosphere, delivering the trifluoroacetylation product with higher chemical efficiency. Furthermore, the method can be turned into a trifluoromethylation protocol by simply changing the reaction parameters. Beyond simple alkenes, this method allows for chemo- and regioselective functionalization of small-molecule drugs and common pharmacophores. Show more
Journal / seriesAngewandte Chemie. International Edition
Pages / Article No.
Subjectlate-stage functionalization; organofluorine compounds; photoredox; radical mechanisms; radical trifluoroacetylation
MoreShow all metadata