Chelation‐Assisted Nickel‐Catalyzed Oxidative Annulation via Double C−H Activation/Alkyne Insertion Reaction

A nickel/NHC system for regioselective oxidative annulation by double C?H bond activation and concomitant alkyne insertion is described. The catalytic reaction requires a bidentate directing group, such as an 8‐aminoquinoline, embedded in the substrate. Various 5,6,7,8‐tetrasubstituted‐N‐(quinolin‐8‐yl)‐1‐naphthamides can be prepared as well as phenanthrene and benzoh]quinoline amide derivatives. Diarylalkynes, dialkylalkynes, and arylalkylalkynes can be used in the system. A Ni⁰/Ni^II catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two‐component coupling partner and as a hydrogen acceptor.