(SCp)Rhodium‐Catalyzed Asymmetric Satoh–Miura Reaction for Building‐up Axial Chirality: Counteranion‐Directed Switching of Reaction Pathways

Abstract Satoh–Miura reaction is an important method for extending π‐systems by forging multi‐substituted benzene rings via double aryl C−H activation and annulation with alkynes. However, the development of highly enantioselective Satoh–Miura reaction remains rather challenging. Herein, we report an asymmetric Satoh–Miura reaction between 1‐aryl benzo[ h ]isoquinolines and internal alkynes enabled by a SCpRh‐catalyst. Judiciously choosing the counteranion of the Rh‐catalyst is crucial for the desired reactivity over the competitive formation of azoniahelicenes. Detailed mechanistic studies support the proposal of counteranion‐directed switching of reaction pathways in Rh‐catalyzed asymmetric C−H activation.