Energy‐Transfer Enabled Divergent Synthesis of Polycyclic γ‐Sultines

Abstract A visible‐light‐initiated energy‐transfer enabled radical cyclization for the divergent synthesis of polycyclic γ‐sultine derivatives has been developed. The reaction provides an alternative and expeditious access to benzofused γ‐sultine frameworks, the analogues of γ‐lactones and γ‐sultones, and features good functional group compatibility, mild reaction conditions and excellent diastereoselectivity. The robustness and application potential of this method have also been successfully displayed by two gram‐scale reactions and the synthesis of polycyclic sultones. Mechanistic studies indicated the transformations through a possible energy‐transfer enabled intramolecular radical homolytic substitution or hydrogen atom transfer process mainly.