Merge of Photoinduced Brook Rearrangement with Epoxidation for the Synthesis of Oxiranes

Oxirane frameworks constitute a privileged class of synthetic motifs due to their widespread utility as key intermediates and final products in pharmaceuticals, agrochemicals, and materials science. Herein, we report a photochemical strategy for the synthesis of oxiranes by merging visible light-induced radical Brook rearrangement with a subsequent epoxidation process. This approach proceeds under exceptionally mild reaction conditions employing fluorescein sodium as a metal-free photocatalyst, allowing for the facile construction of structurally diverse oxiranes. Notably, the reaction exhibits excellent scalability, and the corresponding products are amenable to late-stage functionalization, highlighting its practical synthetic potential. Furthermore, a detailed mechanistic scenario is proposed on the basis of control experiments.