N,N-Bis(trifluoromethyl)aminoacetonitrile: A Versatile Building Block for the Introduction of the Bis(trifluoromethyl)amino Group.

N,N-Bis(trifluoromethyl)aminoacetonitrile (CF)NCHCN (1) that is accessible via a simple single-step protocol is established as a building block for the introduction of the (CF)N group. The two reaction sites of 1, the methylene unit and the nitrile (cyano) group, provide access to different organic substance classes. This includes alkenes via Knoevenagel condensations, and N-heterocycles and acid derivatives obtained by addition reactions to the nitrile unit. These new (CF)N derivatives are potential building blocks containing the bis(trifluoromethyl)amino group. Deprotonation of 1 at the methylene group highlights the electron-withdrawing nature of the (CF)N group. The {(CF)NCHCN} anion (1) is characterized by NMR spectroscopy and its reaction with [PhPAuCl] results in [PhPAuCH{N(CF)}(CN)] (Au1) and [(PhPAu)C{N(CF)}(CN)] (Au1). Crystal structure analysis of (CF)NCHCN (1), Au1, and almost all alkenes, N-heterocycles, and acid derivatives with a (CF)N group combined with spectroscopic data and results from DFT calculations provide insight into properties of the highly fluorinated (CF)N substituent. Especially the ability of the amino nitrogen atom to participate in weak hydrogen bonding, albeit its low basicity, is of relevance.