Photoinduced Peroxide-Mediated Minisci-Type Borylation and Alkylation of <i>N</i> -Heteroarenes with Boranes and Alkyltrifluoroborates

We reported a metal- and photocatalyst-free strategy for visible-light-driven Minisci-type borylation and alkylation of <i>N</i>-heteroarenes via energy transfer (EnT) from photoexcited protonated heteroarenes to peroxides. This method enabled regioselective C-H functionalization using amine/phosphine-borane complexes or alkyltrifluoroborates under mild conditions, providing broad substrate scope and high functional group tolerance. Mechanistic studies confirmed the involvement of radical intermediates and highlight the role of EnT in homolytic O-O cleavage. The process presented a distinct advantage over conventional transition-metal-catalyzed approaches, integrating an improved environmental performance with practical efficiency.