Tetrafluoroethylene-containing azides are accessed in two steps (one pot) from tetrafluoroalkyl bromides by metalation and reaction with electrophilic azides. Subsequent copper(i)-catalyzed azide-alkyne cycloaddition afforded N-tetrafluoroethyl and N-tetrafluoroethylene 4-substituted 1,2,3-triazoles. In addition, the protocol for the synthesis of 4,5-disubstituted 1,2,3-triazoles is presented.

Azidofluoromethane was prepared for the first time by the nucleophilic displacement of bromofluoromethane with sodium azide.