Highly Atroposelective Rhodium(II)-Catalyzed N–H Bond Insertion: Access to Axially Chiral N-Arylindolocarbazoles

The highly atroposelective construction of axially chiral N-arylindolocarbazoles is disclosed via the Rh(II)-catalyzed intermolecular carbene N–H insertion reactions. This straightforward transformation provides a rapid access to a wide range of enantio-enriched N-arylindolocarbazole atropisomers bearing the C–N axis in moderate to good yields and high enantioselectivities. Also, the synthetic utility of this protocol is unambiguously emphasized by the late-stage functionalization (LSF) of some representative natural products and bioactive molecules. Furthermore, the polyaromatic ring construction and N-arylindolocarbazole-derived chiral phosphoric acid (CPA) synthesis also highlight its practical value in materials chemistry and catalytic asymmetric synthesis.