Herein, we report that readily accessible azoxy-triazenes
can serve
as nitrogen atom sources under visible light excitation for the phthalimido-protected
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
multisubstituted 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
the idea that the photofragmentation of azoxy-triazenes results in
the generation of a free singlet nitrene. Furthermore, a mild photoredox-catalyzed
N–N cleavage of the protecting group to furnish the free aziridines
is reported. 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.