Divergent Carbocatalytic Routes in Oxidative Coupling of Benzofused Heteroaryl Dimers: A Mechanistic Update

Mildly thermal air or HNO(3) oxidized activated carbons catalyse oxidative dehydrogenative couplings of benzo[b]fused heteroaryl 2,2’‐dimers, e.g., 2‐(benzofuran‐2‐yl)‐1H‐indole, to chiral 3,3’‐coupled cyclooctatetraenes or carbazole‐type migrative products under O(2) atmosphere. DFT calculations show that the radical cation and the Scholl‐type arenium cation mechanisms lead to different products with 2‐(benzofuran‐2‐yl)‐1H‐indole, being in accord with experimental product distributions.