FLP-Catalyzed Monoselective C-F Functionalization in Polyfluorocarbons at Geminal or Distal Sites.

We report frustrated Lewis pair (FLP)-catalyzed monoselective C-F activation in a range of aliphatic polyfluorocarbons with equivalent geminal and distal C-F positions. This methodology can be applied to aromatic-, ether-, thioether-, and alkyl-supported fluoromethyl groups. We expand the range of FLP base partners that work with monoselective C-F activation to include sulfide. The activated products can be subsequently functionalized via SN2 substitutions, photoredox-alkylations, and Suzuki couplings.