Yi, XiangliMao, RunzeLavrencic, LaraHu, Xile2021-10-232021-10-232021-10-232021-09-2810.1002/anie.202108465https://infoscience.epfl.ch/handle/20.500.14299/182397WOS:000700472500001Polyfluoroarenes are an important class of compounds in medical and material chemistry. The synthesis of alkylated polyfluoroarenes remains challenging. Here we describe a decarboxylative coupling reaction of N-hydroxyphthalimide esters of aliphatic carboxylic acids with polyfluoroaryl zinc reagents (Zn-Ar-F) via synergetic photoredox and copper catalysis. This method readily converts primary and secondary alkyl carboxylic acids into the corresponding polyfluoroaryl compounds, which could have a wide range of F-content (2F-5F) and variable F-substitution patterns on the aryl groups. Broad scope and good functional group compatibility were achieved, including on substrates derived from natural products and pharmaceuticals. Mechanistic study revealed that a [Cu-(Ar-F)(2)] species could be responsible for the transfer of polyfluoroaryl groups to the alkyl radicals.Chemistry, MultidisciplinaryChemistryaliphatic acidcopperphotocatalysispolyfluoroarylationreaction mechanismsredox-active estersf bond activationc-forganozinc reagentsallyl halidesmetalphotoredoxfluorinefunctionalizationalkynylationtext::journal::journal article::research article