Phosphine-Catalyzed Atroposelective Formal [3 + 2] Cycloaddition Desymmetrization of N -Arylmaleimides.

Herein, a new strategy for the enantioselective synthesis of axially chiral N -aryl succinimides was devised by [3 + 2] annulation of MBH carbonates and N -aryl maleimides under chiral phosphine. This desymmetrization process allows for quick construction of both two stereogenic carbon centers and a remote C Ar -N atropisomeric chirality. A series of structurally diverse N -aryl succinimides were obtained with good to excellent yields, diastereoselectivities, and enantioselectivities. The process is mild, efficient, and scalable and features a broad substrate scope.