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

Angew Chem Int Ed Engl. 2023 Jan 16;62(3):e202214460. doi: 10.1002/anie.202214460. Epub 2022 Dec 8.

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.

Keywords: Asymmetric Catalysis; Counteranion; C−H Activation; Rhodium Catalysis; Satoh-Miura Reaction.