Seventeen new highly fluorinated phosphoramidates containing alkylamino moieties of the type (RFO)$_2$P(O)NHR (R = CH$_2$CH$_2$CH$_3$, (CH$_2$)$_3$CH$_3$, (CH$_2$)$_4$-CH$_3$, CH(CH$_3$)$_2$, C$_6$H$_{11}$, CH$_2$CH$_2$-C$_6$H$_5$, CH$_2$-C$_6$H$_5$ or C$_6$H$_5$; RF = CH$_2$CF$_3$, CH$_2$C$_2$F$_5$ or CH$_2$CH$_2$C$_6$F$_{13}$) were synthesized. These compounds were obtained through the reaction of primary amines with bis(polyfluoroalkyl)phosphites as phosphorylating agents, using molecular iodine as a mild catalyst and in the presence of H$_2$O$_2$.This method was chosen out of various literature common methods, which were thoroughly investigated using $^{31}$P NMR spectroscopy. In addition, the variation in reaction rates among different phosphites was studied and compared with previous research findings. The title phosphoramidates were fully characterized using multinuclear ($^1$H, $^{13}$C, $^{31}$P, and $^{19}$F) NMR, IR, and HRMS techniques.