Fe-Catalyzed Alkylazidation of α-Trifluoromethylalkenes: An Access to Quaternary Stereocenters Containing CF 3 and N 3 Groups.

A concise Fe-catalyzed alkylazidation of α-trifluoromethylalkenes via a C-C bond cleavage/radical addition/azidation cascade is described. This protocol features a broad substrate scope, excellent functional group compatibility, and the ability to be performed on a gram scale, thus offering a practical and step-economic approach to the synthetically useful tertiary α-trifluoromethyl azides.