Affiliation:
1. Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo náměstí 2 166 00 Prague 6 Czech Republic
2. Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030/8 128 43 Prague Czech Republic
3. Department of Physical Chemistry University of Chemistry and Technology Technická 5 166 28 Prague Czech Republic
Abstract
AbstractN‐Trifluoromethylated organics may be applied in drug design, agrochemical synthesis, and materials science, among other areas. Yet, despite recent advances in the synthesis of aliphatic, cyclic and heterocyclic N‐trifluoromethyl compounds, no strategy based on trifluoromethyl nitrene has hitherto been explored. Here we describe the formation of triplet trifluoromethyl nitrene from azidotrifluoromethane, a stable and safe‐to‐use precursor, by visible light photocatalysis. The addition of CF3N to alkenes via biradical intermediates afforded previously unknown aziridines substituted with trifluoromethyl group on the nitrogen atom. The obtained aziridines were converted into either N‐trifluoromethylimidazolines, via formal [3+2] cycloaddition with nitriles, mediated by a Lewis acid, or into N‐trifluoromethylaldimines, via ring opening and aryl group migration mediated by a strong Brønsted acid. Our findings open new opportunities for the development of novel classes of N‐CF3 compounds with possible applications in the life sciences.
Funder
Ústav organické chemie a biochemie Akademie věd České republiky
Grantová Agentura České Republiky
Ministerstvo Školství, Mládeže a Tělovýchovy