Visible-light-induced trifluoromethylationr eactions of alkenesw ith CF 3 Ii nt he presence of Nile red, which acted as an organic photosensitizer,h ave been developed. Compared to trifluoromethylations with transition-metal-based photosensitizers like Ru and Ir complexes, the use of Nile red made this process more environmentally benign, not only by avoiding issues associated with metal residues,b ut also by allowing the use of low-energyp hotons (yellow LEDs) owing to its light absorbance at long wavelengths (440-600 nm). In the process, trifluoromethylated alkene and trifluoromethylated iodoalkane products were selectively synthesized by controlling the reaction conditions. In particular,t he base employed significantly affected the selectivity of the process. The iodotrifluoromethylation of alkynes and the trifluoromethylation of N-heterocycles also proceeded well using Nile red. Furthermore, it was found that a CCF 3 radical could be generatedi nt he absence of Nile red under ah igher photon energy by visible-light-induced electron transfer between tertiarya mines andC F 3 I, despite the lower reactivity.

(Hetero)aryloxytetrafluoroethylation of heteroaromatics and alkenes has been achieved by visible-light photocatalysis utilizing readily synthesized oxyfluoroalkyl reagents. The mild reaction conditions and the high diversity on both substrates and oxyfluoroalkyl reagents make this a useful method for late-stage modifications in the development of various functional molecules.