Rh-Catalyzed Denitrogenative Formal (3 + 2) Cycloaddition for the Synthesis of Remote Chiral C–N and N–N Atropisomers

Herein, we report a catalytic denitrogenative annulation strategy for the asymmetric construction of sulfur-containing polycyclic frameworks with remote axial chirality. Using N-aryl maleimides as axially prechiral alkenes, the transformation proceeds via a catalytic desymmetrization pathway, enabling the simultaneous formation of multiple contiguous carbon stereocenters and a distal axial chiral element in a single step, with excellent stereocontrol (up to >99% ee and high diastereoselectivity). The reaction exhibits broad substrate scope and operates under mild conditions, affording structurally diverse axially chiral heterocycles in high yields. This denitrogenative desymmetrization strategy thus provides a general and practical platform for the efficient synthesis of remote axially chiral sulfur-containing molecules.