Rhodium-Catalyzed Atroposelective C–H Arylation of (Hetero)Arenes Using Carbene Precursors as Arylating Reagents

Rhodium­(III)-catalyzed C–H activation-based arylation of sterically hindered (hetero)­arenes has been realized using diazo compounds and triazoles as arylating reagents for atroposelective synthesis of two classes of biaryls. The coupling of 3-substituted indoles and N-sulfonyl­triazoles afforded indoles with a C(2)–C chiral axis, while the arylation of 1-naphthyl­thioether with ortho-quinone diazide afforded chiral binaphthyls. These coupling systems proceeded under mild conditions via C–H activation and carbene insertion despite the steric hindrance of both the arenes and the carbene precursors.