Chemistry of Bis(trifluoromethyl)amines: Synthesis, Properties, and Applications

Fluorinated groups are widely applied substituents in medicinal and agricultural chemistry as well as materials sciences because the introduction of per- and polyfluorinated substituents allow the targeted tuning of molecules and materials properties, in general. In addition to per- and polyfluoroalkyl substituents, especially trifluoromethylheteroatom substituents have attracted increasing interest in recent years. The bis(trifluoromethyl)amino group (CF₃)₂N is an example for a trifluoromethylheteroatom substituent. It has been known since the middle of the last century and it has been used and tested in different fields of applications. This review summarizes the chemistry of the bis(trifluoromethyl)amino group since its beginning up to the end of 2024. It focuses on the synthesis of (CF₃)₂N-containing compounds, precursors for the introduction of the (CF₃)₂N group, and follow-up reactions of (CF₃)₂N-containing molecules. The physicochemical properties of the (CF₃)₂N group and of bis(trifluoromethyl)amines are collected and potential applications that have been described are summarized, as well.