Rh-Catalyzed Coupling Reactions of Fluoroalkyl N -Sulfonylhydrazones with Azides Leading to α-Trifluoroethylated Imines.

Herein we describe the pioneering Rh-catalyzed coupling reactions of a fluoroalkyl carbene with azides to access α-trifluoroethylated imines, where fluoroalkyl N -sulfonylhydrazones are used as fluoroalkyl diazo surrogates. Remarkably, using TMSN 3 as the N source, two C-N bond formation products were obtained. Furthermore, the α-trifluoroethylated imine products could be easily reduced to the corresponding N -trifluoroethylated anilines. Experimental results and theoretical calculations justify a stepwise reaction pathway involving the formation of rhodium carbene, the addition of HN 3 , and C═N bond formation.