Base-Controlled Regiodivergent Azidation of Trifluoromethyl Alkenyl Triflates: Transition-Metal-Free Access to CF₃‑Containing Allyl Azides and Alkenyl Azides

A base-controlled regiodivergent azidation of trifluoromethyl alkenyl triflates providing either (E)-3-azido-1-aryl-4,4,4-trifluorobut-1-ene (CF₃-containing allyl azides) or (Z)-1-azido-1-aryl-4,4,4-trifluorobut-1-ene (CF₃-containing alkenyl azides) is described. Catalyzed by Et₃N, the azidation of trifluoromethyl alkenyl triflates with TMSN₃ gave CF₃-containing allyl azides. On the other hand, using stoichiometric DBU, the regioisomeric azidation products, CF₃-containing alkenyl azides, were obtained in good yield. A further transformation for CF₃-containing amines, triazoles, and azirines highlights the practical applicability of this transition-metal-free protocol.