Visible-light-induced, iridium catalyzed, para-selective C–H difluoroalkylation of aniline derivatives under mild reaction conditions is reported. Various substrates and bioactive compounds, such as precursors of vorinostat and chlorpropham, were all well tolerated. This protocol features a wide substrate scope, high regioselectivity, low catalyst usage, and operational simplicity.

The direct incorporation of a trifluoromethyl group on an aromatic ring using a radical pathway has been extensively investigated. However, the direct highly para‐selective C−H trifluoromethylation of a class of arenes has not been achieved. In this study, we report a light‐promoted 4,5‐dichlorofluorescein (DCFS)‐enabled para‐selective C−H trifluoromethylation of arylcarbamates using Langlois reagent. The preliminary mechanistic study revealed that the activated organic photocatalyst coordinated with the arylcarbamate led to para‐selective C−H trifluoromethylation. Ten‐gram scale reaction performs well highlighting the synthetic importance of this new protocol.

The direct incorporation of a trifluoromethyl group on an aromatic ring using a radical pathway has been extensively investigated. However, the direct highly para‐selective C−H trifluoromethylation of a class of arenes has not been achieved. In this study, we report a light‐promoted 4,5‐dichlorofluorescein (DCFS)‐enabled para‐selective C−H trifluoromethylation of arylcarbamates using Langlois reagent. The preliminary mechanistic study revealed that the activated organic photocatalyst coordinated with the arylcarbamate led to para‐selective C−H trifluoromethylation. Ten‐gram scale reaction performs well highlighting the synthetic importance of this new protocol.