Site‐Selective Oxidative Dimerization of Oxaphenalenone Scaffolds: Total Synthesis of (±)‐Bacillosporin C

A general and mechanistically elucidated approach to the total synthesis of the dimeric oxaphenalenone natural product bacillosporin C, a member of the duclauxin family, is reported. A key feature of this strategy is the realization of a site‐selective oxidative dimerization of the oxaphenalenone monomer. This dimerization can be achieved either by an iron‐catalyzed approach or, more efficiently, through an electrochemical oxidative dimerization. Notably, the latter enables a controlled single‐electron oxidation, leading to the selective formation of the dimer while suppressing overoxidation. Detailed mechanistic investigations, including cyclic voltammetry, density functional theory calculations, and a series of control experiments, revealed that the key dimerization process proceeds predominantly through a radical‐mediated pathway.