General Access to N−CF₃ Secondary Amines and Their Transformation to N−CF₃ Sulfonamides

Abstract

The synthesis of N−CF3 compounds through fluorination or trifluoromethylation of N‐containing compounds has been extensively investigated. However, general access to N−CF3 compounds simply from N−CF3 secondary amines is hampered by the challenging preparation and instability of these amines, as well as a much lower reactivity due to the strong electron‐withdrawing nature and steric bulk of the trifluoromethyl moiety. Herein, we report a general and highly efficient synthesis of N−CF3 secondary amines with excellent isolated yields via the addition of the in situ generated difluoromethyl imine (R−N=CF2) intermediates with hydrogen fluoride, which is mildly produced by triethylsilane and silver fluoride. N−CF3 sulfonamides, highly desirable but scarce at present, are easily accessible from these valuable building blocks through an unprecedented route. This study will bring new vitality to the synthesis of N−CF3 compounds.

Fluorine‐Containing Functional Group‐Based Energetic Materials

“…The trifluoromethyl moiety (CF 3 ) is a significant group in organic synthesis and drug chemistry, as well as in the realm of energetic materials [39,82–85] . The introduction of the trifluoromethyl group increases the density, enhances the thermal stability, and improves sensitivity owing to the excellent properties of the three fluorine atoms bonded to the carbon center [86–88] .…”

“…The trifluoromethyl moiety (CF 3 ) is a significant group in organic synthesis and drug chemistry, as well as in the realm of energetic materials. [39,[82][83][84][85] The introduction of the trifluoromethyl group increases the density, enhances the thermal stability, and improves sensitivity owing to the excellent properties of the three fluorine atoms bonded to the carbon center. [86][87][88] The improvement of the detonation performance of trifluoromethyl group-based materials is yet to be fully explored, unlike the F and NF 2 substituted trinitromethyl groups discussed earlier.…”