Visible‐Light‐Induced Site‐Selective C(sp ² /sp ³ )‐H Functionalization toward Epoxides

Comprehensive Summary This work presents the first practical and modular strategy for visible‐light‐induced, site‐selective C(sp 2 /sp 3 )‐H functionalization of inert C–H bonds in feedstock chemicals. Utilizing tetrabutylammonium decatungstate (TBADT) as a hydrogen atom transfer photocatalyst, a broad range of substrates, including ethers, thioethers, amides, alkanes, aldehydes, and complex bio‐related molecules, undergo efficient epoxidation with allylic peroxides under mild, oxidant‐free, and operationally simple conditions. The protocol affords diverse, highly functionalized oxiranes with excellent site‐selectivity and wide functional group tolerance at room temperature under 390 nm light irradiation. Its synthetic utility is further demonstrated by gram‐scale synthesis and versatile post‐transformations, such as ring‐opening, reduction, halogenation, azidation, and one‐pot cyclizations. Molecular docking studies reveal that the resulting epoxides exhibit favorable binding interactions with kinase proteins, highlighting potential applications in biochemical research and drug development. This visible‐light‐mediated C–H epoxidation offers a green, efficient, and modular route to high‐value oxiranes, expanding the toolkit for organic synthesis and medicinal chemistry.