Trifluoromethanesulfenamides (CF₃SN-molecules) are interesting products for further applications. In particular, the presence of the CF₃SN group can contribute to increase their lipophilicity. The better way to obtain such products is the direct trifluoromethylthiolation of the corresponding amines. Herein, an efficient method under mild conditions (room temperature, iodide catalysis) is described to obtain the expected trifluoromethanesulfenamides in a late-stage functionalization. This method is based on the use of the reagent BB23 (N-tosyl, N-methyltrifluoromethanesulfenamide), demonstrating the high versatility and polyvalence of this reagent in organofluorine chemistry. Some bioactive elaborated compounds were successfully functionalized.