Expedient Trifluoromethylacylation of Styrenes Enabled by Photoredox Catalysis

Comprehensive Summary Herein, we disclosed a photoredox enabled protocol for trifluoromethylacylation of styrenes through a radical‐carboanion cascade and subsequent oxidation. With a broad range of aldehydes and inexpensive Langlois reagent as acyl and CF 3 precursor, respectively, the alkene motif could be readily converted into β‐trifluoromethyl ketones in moderate to good yields and with excellent regioselectivity. Besides CF 3 , di‐, mono‐ and non‐fluorinated C‐radicals were revealed amenable in this reaction, providing good opportunity for the construction of structurally diverse ketones of interest in pharmaceutical research. Additionally, the utility of this protocol was further demonstrated by successful extension to trifluoromethylarylation and ‐alkylation by employing arylcyanide or acrylates in place of carbonyls.