Abstract The development of an efficient alternative to the widely employed Balz‐Schiemann deaminative fluorination method (i. e. without using aryl diazonium tetrafluoroborate salt) is a challenging task. Herein, we report a convenient one‐pot method for the FeCl 3 ‐nanocellullose mediated mechanochemical synthesis of fluoroarenes through the selective substitution of an aromatic amino group by fluorine group using pyrylium tetrafluoroborate (Pyry‐BF 4 ) and sodium fluoride (NaF) via in situ formation of pyridinium salt intermediate. The scope of the present protocol includes synthesis of thirty‐four organofluorine compounds with excellent yields via a selective substitution (S N Ar) of an amino group by fluorine. The presented concise methodology opens a pathway to access new chemical spaces for the late‐stage functionalization in pharmaceutical industries.
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