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.