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. 2021 Jul 26;27(42):10973-10978.
doi: 10.1002/chem.202101436. Epub 2021 Jun 9.

Stable and Storable N(CF3 )2 Transfer Reagents

Leon N Schneider  1 , Eva-Maria Tanzer Krauel  2 , Carl Deutsch  3 , Klaus Urbahns  3 , Tobias Bischof  1 , Kristina A M Maibom  1 , Johannes Landmann  1 , Fabian Keppner  1 , Christoph Kerpen  1 , Michael Hailmann  1 , Ludwig Zapf  1 , Tanja Knuplez  1 , Rüdiger Bertermann  1 , Nikolai V Ignat'ev  1 , Maik Finze  1
Affiliations

Stable and Storable N(CF3 )2 Transfer Reagents

Leon N Schneider et al. Chemistry. .

Abstract

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(CF3 )2 group are rare. One reason is that transfer reagents are scarce and metal-based storable reagents are unknown. Herein, a set of CuI and AgI 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.

Keywords: N ligands; amination; copper; fluorinated ligands; silver.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Top: Comparison of the availability of CuI and AgI complexes. Middle: Two‐step synthesis of salts of the N(CF3)2 − ion by electrochemical fluorination (ECF) of CF3SO2N(CH3)2.[16, 17] Bottom: Decomposition sequence of the N(CF3)2 − ion via perfluoroazapropene to give CF3N=CF−N(CF3)2.
Figure 2
Figure 2
Synthesis and crystal structures of the copper(I) complexes 1  a−1  e (thermal ellipsoids set at 25 % probability; H atoms are omitted for clarity; C atoms of the N‐ and P‐donor ligands are depicted as stick models).
Figure 3
Figure 3
Synthesis and crystal structures of the silver(I) complexes 2  a−2  c, 2  f and of the complex silver(I) salt 3 (thermal ellipsoids set at 25 % probability; H atoms are omitted for clarity; C atoms of the N‐ and P‐donor ligands are depicted as stick models).
Figure 4
Figure 4
Synthesis of bis(trifluoromethyl)methyl arenes and crystal structures of 5 and 7.
Figure 5
Figure 5
Synthesis of 2‐bis(trifluoromethyl)amino acetate (8  a), its conversion into N,N‐bis(trifluoromethyl)glycine (8  b), and the crystal structure of 8  b (thermal ellipsoids set at 30 % probability; H atoms are omitted for clarity).
Scheme 1
Scheme 1
Sandmeyer‐type reaction of 1  d giving 9 (yield of 9 determined by 19F NMR spectroscopy with benzotrifluoride as internal standard).
See this image and copyright information in PMC

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