Atroposelective Synthesis of Pyridoindolones Bearing Two Remote Distinct C–N Axes through Cobalt-Catalyzed Enantioselective C–H Activation

C-N axially chiral compounds represent an important class of atropisomers that are prevalent in bioactive and material molecules. Despite recent advances in synthetic methodologies, the asymmetric construction of atropisomers featuring multiple C-N axes has been rarely explored, significantly limiting their further applications. Herein, we report a novel atroposelective synthesis of diaxially chiral pyridoindolones featuring both six-five and six-six C-N axes through cobalt-catalyzed asymmetric C-H annulation. This approach demonstrates exceptional efficiency, yielding a diverse array of chiral pyridoindolones with excellent yields and atroposelectivities (60 examples, up to >99% yield, >99% ee, and >20:1 dr). Mechanistic studies revealed that the stereochemistry of both C-N axes were generated and fixed simultaneously during the C-H cyclometalation step, along with an unexpected asymmetric amplification effect. The practicality of this protocol is further underscored by successful gram-scale syntheses and various transformations, including the formation of a chiral phosphine ligand. Notably, exceptional photoluminescence quantum yields (<i>Φ</i>_F up to 0.99) and positive solvatochromism were observed, coupled with significant chiroptical properties, underscoring the potential applications of these compounds in organic fluorescent materials.