Litcius/Paper detail

Photocatalytic Generation of Trifluoromethyl Nitrene for Alkene Aziridination

Norbert Baris, Martin Dračínský, Ján Tarábek, Josef Filgas, Petr Slavı́ček, Lucie Ludvíková, Soňa Boháčová, Tomáš Slanina, Blanka Klepetářová, Petr Beier

2023Angewandte Chemie International Edition43 citationsDOIOpen Access PDF

Abstract

Abstract N ‐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 CF 3 N 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 ‐CF 3 compounds with possible applications in the life sciences.

Topics & Concepts

NitreneTrifluoromethylAlkeneChemistryPhotocatalysisCombinatorial chemistryCycloadditionLewis acids and basesRing (chemistry)PhotochemistryOrganic chemistryMedicinal chemistryCatalysisAlkylFluorine in Organic ChemistrySynthesis and Catalytic ReactionsRadical Photochemical Reactions
Photocatalytic Generation of Trifluoromethyl Nitrene for Alkene Aziridination | Litcius