Direct CH Bond Halogenation of Cubane Skeleton Mediated by Photocatalysis

The synthesis of multisubstituted cubane derivatives remains challenging due to the limitations of current synthetic methods. Therefore, developing site‐selective CH halogenation reactions starting from simple 1,4‐substituted cubane compounds is highly desirable. Herein, we report an efficient strategy for the CH halogenation of cubane using sodium decatungstate (NaDT) as a hydrogen atom transfer photocatalyst to produce cubyl radicals which could undergo halogenation with different halogen sources to achieve chloro‐, bromo‐, and iodo‐substituted cubane derivatives in poor‐to‐excellent yields ranging from 12% to 94%. This method offers a practical route for accessing multifunctionalized cubanes for further research.