摘要

The atroposelective synthesis of atropisomers with vicinal diaxes remains rare and challenging, due to the steric influence between the two axes and their unique topology. Herein, we disclose a single‐step construction of atropisomers with vicinal C?C and C?N chiral diaxes by cyclopentadiene (Cp)‐free cobalt‐catalyzed intramolecular atroposelective C?H annulation, providing the desired diaxial atropisomers of unique structures with decent stereocontrols of both axes (up to >99?% ee and 70?:?1 dr). The optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being candidate materials for potential CPL applications. Atropisomerization experiments and density function theory (DFT) calculations are conducted to study the rotational barriers and rotation pathways of the diaxes.(#br)A single‐step construction of atropisomers with vicinal C?C and C?N chiral diaxes by cyclopentadiene (Cp)‐free cobalt‐catalyzed intramolecular atroposelective C?H annulation with decent stereocontrols (up to >99?% ee and 70/1 dr) was reported. Atropisomerization experiments and DFT calculations are done to study the rotational barriers and pathways of the diaxes.