Selective C4−F bond cleavage/C−O bond formation of polyfluoroarenes with phenols and benzyl alcohols

•An easy metal-free access to polyfluoroarylated ethers.•SNAr reaction of phenols/benzyl alcohols with pentafluorobenzene via selective C4–F bond cleavage.•Other polyfluoroarenes and the long-chain aliphatic alcohols were suitable for the reaction.•Polyfluoroary heterocyclic compound could be created with this method.

A facile and efficient SNAr method for the synthesis of unsymmetrical polyfluoroaryl ethers via selective C4–F bond cleavage of pentafluorobenzene is reported. The reaction could proceed smoothly without the requirement of additional metals or ligands, and afford a series of the corresponding products in good to high yields. A wide variety of substituted phenols and alcohols provided 1,2,4,5-tetrafluoropheny ether derivatives in regioselective manner.

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