One-pot synthesis of trifluoromethyl amines and perfluoroalkyl amines with CF₃SO₂Na and R_fSO₂Na

Abstract

Novel use of CF3SO2Na and RfSO2Na for the synthesis of trifluoromethyl amines and perfluoroalkyl amines was developed.

A Facile and Inexpensive Way to Synthesize N‐trifluoromethyl Compounds

“…For a real test of our procedure, we chose t ert ‐butyl piperazine‐1‐carboxylate ( 12 ) that had been used previously, [2,9] and successfully obtained the N ‐trifluoromethyl analogue 13 in decent yields with our method. In contrast to the former reports, in which the product was described as an oil, we could isolate it as a crystalline colorless substance, clearly demonstrating one of the advantages of our method for this particular substrate.…”

“…A similar process had been observed previously for the synthesis of CF 3 -ethers, [4b,8] however, to the best of our knowl-edge, the reaction of monomeric N-dithiocarbamate-organyls and their conversion via AgF to N-CF 3 groups had not been reported so far. [1b] For a real test of our procedure, we chose tert-butyl piperazine-1-carboxylate (12) that had been used previously, [2,9] and successfully obtained the N-trifluoromethyl analogue 13 in decent yields with our method. In contrast to the former reports, in which the product was described as an oil, we could isolate it as a crystalline colorless substance, clearly demonstrating one of the advantages of our method for this particular substrate.…”

Stable and Storable N(CF3)2 Transfer Reagents

“…In contrast to perfluoroalkyl and perfluoroalkoxy groups, the chemistry of related perfluoroalkyl nitrogen substituents has been studied to a much lesser extent. Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years [28–38] . Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials [18,39–40] .…”

“…Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years. [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ] Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials. [ 18 , 39 , 40 ] Especially the N , N ‐bis(trifluoromethyl)amino group is of interest as its organic derivatives are known to exhibit high stability, for example against acids and bases,[ 1 , 41 ] and because its potential as substituent in pharmaceuticals was demonstrated, earlier.…”

Direct Synthesis of Thiocarbamoyl Fluorides and Trifluoromethylamines Through Fluorinative Desulfurization

“…The latter can also be generated starting from AgSCF 3 in conjunction with potassium bromide (Scheme , III ). More recently, the group of Jiang and Yi demonstrated that the Langlois reagent could also be used in conjunction with triphenylphosphine to form thiocarbamoyl fluorides (Scheme , IV ) . In this context, we thought that the straightforward synthesis of thiocarbamoyl fluoride through fluorinative desulfurization would constitute an attractive option for the access thiocarbamoyl fluorides.…”