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The synthesis of alkylated polyfluoroarenes remains challenging. Here we describe a decarboxylative coupling reaction of N\u2010hydroxyphthalimide esters of aliphatic carboxylic acids with polyfluoroaryl zinc reagents (Zn\u2010Ar<jats:sub>F<\/jats:sub>) 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\u2010content (2F\u20105F) and variable F\u2010substitution 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\u2010(Ar<jats:sub>F<\/jats:sub>)<jats:sub>2<\/jats:sub>] species could be responsible for the transfer of polyfluoroaryl groups to the alkyl radicals.<\/jats:p>","DOI":"10.1002\/anie.202108465","type":"journal-article","created":{"date-parts":[[2021,9,1]],"date-time":"2021-09-01T15:41:11Z","timestamp":1630510871000},"page":"23557-23563","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":42,"title":["Photocatalytic Decarboxylative Coupling of Aliphatic N\u2010hydroxyphthalimide Esters with Polyfluoroaryl Nucleophiles"],"prefix":"10.1002","volume":"60","author":[{"given":"Xiangli","family":"Yi","sequence":"first","affiliation":[{"name":"Laboratory of Inorganic Synthesis and Catalysis Institute of Chemical Sciences and Engineering Ecole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL)  ISIC-LSCI, BCH 3305 1015 Lausanne 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