Asymmetric Convergent Assembly of Atropisomers Bearing Three Chiral Elements via Rhodium-Catalyzed Conjugate Addition

Abstract Atropisomers bearing multiple chiral elements offer diverse molecular architectures for the development of functional molecules; however, their catalytic asymmetric synthesis remains highly challenging. In this work, we report a catalytic asymmetric method for the efficient synthesis of atropisomers bearing three distinct chiral elements. This method employs a chiral rhodium catalyst to simultaneously control the stereodynamic axis of biarylhemiboronic esters, the remote desymmetrization of proatropisomeric maleimides, and the construction of a carbon stereocenter, affording chiral products containing a chiral C–C axis, a chiral C–N or N–N axis, and a carbon stereocenter in high yields with high stereoselectivities. Furthermore, we demonstrated the utility of the resulting scaffold through product derivatization and the development of an azophenol-based intramolecular charge-transfer probe. Finally, density functional theory (DFT) calculations were employed to elucidate the stereochemical control of the reaction.