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A novel green and efficient reaction route for the synthesis of 2‐chloroquinoline via N‐fluoride fluorinated by 1‐Chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo [2.2.2] octane bis(tetrafluoroborate) (Selectfluor) with 1,3‐Dichloro‐5,5‐dimethylhydantoin (DCDMH) in Vapourtec reactor has been developed. In addition, a series of C2 heterocyclic derivative products are obtained in moderate to good yields under no metal conditions.