Remote Generation of Pyramidalized N–N Axial Chirality via a Copper-Catalyzed Friedel–Crafts Reaction

We report a Cu/bisoxazoline-catalyzed desymmetrization via Friedel–Crafts alkylation, facilitating the remote construction of N–N axial chirality with a central carbon stereocenter. The operational robustness is underscored by scale-up reactions and versatile postsynthetic transformations. X-ray crystallography verifies a pyramidalized nitrogen center deviating 20° from planarity, while thermal racemization experiments establish strong configurational stability. This strategy provides a general platform for developing pyramidalized N–N atropisomers.