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Facilitated by an electron donor–acceptor (EDA) complex, an efficient β-trifluoromethylation and perfluoroalkylation of enamides with Togni reagent or perfluoroalkyl iodides is presented under transition-metal-free, photocatalyst-free and mild reaction conditions. Notably, using this photocatalyst-free strategy, direct trifluoromethylation and perfluoroalkylation of quinoxalin-2(1H)-one derivatives was also achieved via a photoactive electron donor–acceptor complex.

Graphical abstract: An electron donor–acceptor complex-initiated C–H trifluoromethylation and perfluoroalkylation of enamides and quinoxalinones

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