Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Abstract

Herein, we report that readily accessible azoxy-triazenes can serve as nitrogen atom sources under visible-light excitation for the efficient aziridination of alkenes. This approach eliminates the need for external oxidants, precious transition metals, and photocatalysts, marking a departure from conventional methods. The versatility of this transformation extends to the selective aziridination of both activated and unactivated multi-substituted alkenes of varying electronic profiles. Notably, this process avoids the formation of competing C–H insertion products. The described protocol is operationally simple, scalable, and adaptable to photoflow conditions. Mechanistic studies support that the photofragmentation of azoxy-triazenes results in the generation of a free singlet nitrene that governs the observed chemoselectivity and stereospecificity of the reaction. Our findings contribute to the advancement of sustainable and practical methodologies for the synthesis of nitrogen-containing compounds, showcasing the potential for broader applications in synthetic chemistry.