Iron(II)-Catalyzed Azidotrifluoromethylation of Olefins and N-Heterocycles for Expedient Vicinal Trifluoromethyl Amine Synthesis

We report herein an iron-catalyzed azidotri-fluoromethylation method for expedient vicinal trifluoromethyl primary-amine synthesis. This method is effective for a broad range of olefins and N-heterocycles, and it facilitates efficient synthesis of a wide variety of vicinal trifluoromethyl primary amines, including those that prove difficult to synthesize with existing approaches. Our preliminary mechanistic studies revealed that the catalyst-promoted azido-group transfer proceeds through a carbo-radical instead of a carbocation species. Characterization of an active iron catalyst through X-ray crystallographic studies suggests that structurally novel iron-azide complexes promote the oxidant activation and selective azido-group transfer