Copper-Catalyzed Innate Ethoxycarbon­yldifluoromethylation of Electron-Rich ­Arenes

We report the direct introduction of the CF2CO2Et moiety into electron‐rich arenes. The copper‐catalyzed process uses commercially available and inexpensive BrCF2CO2Et as a fluorinated building block. This radical‐free reaction proceeds smoothly to give the desired difluoromethylated arenes in modest to good yields with a Friedel–Crafts‐type regioselectivity. The direct introduction of α,α‐difluoromethylated amides was also investigated, and this gave the corresponding difluoromethylated arenes, albeit in moderate yields. This method represents the first transition‐metal‐catalyzed direct introduction of a functionalized fluorinated moiety into electron‐rich arenes. Readily available BrCF2CO2Et is used to introduce a fluorine‐containing group into electron‐rich arenes. This radical‐free transformation proceeds through a CuI/CuIII cycle, and was applied to a wide range of anisole and aniline derivatives.