Rhodium‐Catalyzed ortho ‐Selective CF Bond Borylation of Polyfluoroarenes with BpinBpin

An ortho‐selective CF bond borylation between N‐heterocycle‐substituted polyfluoroarenes and Bpin‐Bpin with simple and commercially available [Rh(cod) 2 ]BF 4 as a catalyst is now reported. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, even toward monofluoroarene, thus providing a facile access to a wide range of borylated fluoroarenes that are useful for photoelectronic materials. Preliminary mechanistic studies reveal that a Rh III/V catalytic cycle via a key intermediate rhodium(III) hydride complex [(H)Rh III L n (Bpin)] may be involved in the reaction.