Nickel‐Catalyzed 1,1‐Difluoroethylation of (Hetero)aryl Halides with 1,1‐Difluoroethyl Chloride (CH 3 CF 2 Cl)

1,1‐Difluoroethylated aromatic compounds are of increasing importance in agrochemicals and pharmaceuticals. The direct introduction of difluoroethyl (CF 2 CH 3 ) group(s) onto aromatic rings using CH 3 CF 2 Cl, an inexpensive and available raw material, still remains a great challenge because of the relatively inert C−Cl bond of CH 3 CF 2 Cl. Herein, we disclose a nickel‐catalyzed 1,1‐difluoroethylation of (hetero)aryl halides with CH 3 CF 2 Cl. The reaction exhibits good functional‐group tolerance and is regarded as a practical method for synthesis of (1,1‐difluoroethyl)arenes.