Kinetic Resolution Approach to the Synthesis of C-N Axially Chiral N -Aryl Aminomaleimides via NHC-Catalyzed [3 + 3] Annulation.

Chiral NHC-catalyzed kinetic resolution of N -aryl aminomaleimides allowing the synthesis of C-N axially chiral N -aryl aminomaleimides via remote chirality control is presented. The catalytically generated α,β-unsaturated acylazoliums from 2-bromoenals underwent selective [3 + 3] annulation with one of the enantiomers of maleimide to furnish fused-dihydropyridinone (bearing axial/central chirality, up to 6:1 dr, >99:1 er) leaving the enantioenriched opposite enantiomer (up to >99:1 er). Studies on C-N bond rotation barrier and dependence on temperature are also provided.