Azidoperfluoroalkanes: Synthesis and Application in Copper(I)‐Catalyzed Azide–Alkyne Cycloaddition

Abstract We report an efficient and scalable synthesis of azidotrifluoromethane (CF 3 N 3 ) and longer perfluorocarbon‐chain analogues (R F N 3 ; R F =C 2 F 5 , n C 3 F 7 , n C 8 F 17 ), which enables the direct insertion of CF 3 and perfluoroalkyl groups into triazole ring systems. The azidoperfluoroalkanes show good reactivity with terminal alkynes in copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC), giving access to rare and stable N ‐perfluoroalkyl triazoles. Azidoperfluoroalkanes are thermally stable and the efficiency of their preparation should be attractive for discovery programs.