A CuBr 2 -catalyzed annulation of 2-bromo-N-arylbenzimidamide with selenium/sulfur powder for the synthesis of benzo[d]isoselenazole and benzo [d]isothiazole in generally good yields was investigated. This synthetic strategy features good substrate scope and functional group tolerance. Furthermore, the corresponding products could be converted into N-aryl indoles via rhodium III -catalyzed ortho C−H activation of the N-phenyl ring, providing an efficient approach for axial aromatic molecules.

Comprehensive Summary A three‐component synthesis of benzo[α]phenanthridines from aromatic aldehydes, cyclohexanones, and aromatic amines has been developed, which is mediated by KI/DMSO/camphorsulfonic acid to afford a variety of functionalized benzo[α]phenanthridines in satisfactory yields. The present strategy provides a biaryl motif ortho to the nitrogen atom which has the potential to be used as ligand by further modification. With the advantages of readily available starting materials, transition‐metal‐free conditions, gram‐scale synthesis, and broad substrate scope, this three‐component protocol provides an efficient approach for the preparation of diverse benzo[α]phenanthridines.