Stable and Storable N(CF(3))(2) Transfer Reagents

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl)amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF(3))(2) group are rare. One reason is that transfer reagents are scarce and metal‐based storable reagents are unknown. Herein, a set of Cu(I) and Ag(I) bis(trifluoromethyl)amido complexes stabilized by N‐ and P‐donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl)amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis(trifluoromethyl)amines, 2‐bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N‐bis(trifluoromethyl)glycine.