Catalytic Generation of Remote C–N Axial Chirality through Atroposelective <i>de novo</i> Arene Construction

The first atroposelective desymmetrization of prochiral N-aryl maleimides through its conversion to axially chiral phthalimides is developed by applying a de novo arene construction strategy. Catalyzed by bis(3,5-dimethylphenyl)prolinol TMS-ether, this reaction proceeds through oxidative [4 + 2]-cycloaddition with α,β-unsaturated aldehydes to generate only a chiral C-N axis remote from the reaction sites with excellent enantioselectivity (up to 97.5:2.5 er).