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A novel Pd(OAc)2–NFSI–TFA system was developed for the highly selective ortho-monofluorination directed by diverse aryl-N-heterocyclic directing groups e.g., quinoxaline, pyrazole, benzo[d]oxazole, and pyrazine derivatives. A Pd(II/IV) catalytic cycle was proposed based on the ESI-MS/MS studies.

Graphical abstract: Pd(OAc)2-catalyzed regioselective aromatic C–H bond fluorination

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