Photoinduced Radical Epoxidation of N-Alkoxyphthalimides with Allylic Peroxides.

A visible-light-driven, site-selective C(sp3)-H functionalization reaction was developed, which couples N-alkoxyphthalimides with readily available allylic peroxides to provide diverse epoxy alcohols under mild conditions without external oxidants. The sequence involves photoexcitation to generate oxygen-centered radicals, intramolecular 1,5-HAT to form remote carbon-centered radicals, and a subsequent radical homolytic-substitution cyclization to furnish the epoxide products. This operationally simple, modular protocol tolerates a broad range of functional groups, accepts varied N-alkoxyphthalimides and peroxide partners, and is amenable to scale-up and diversity-oriented synthesis, highlighting its potential for the assembly of complex molecules.