Sulfenate anion catalyzed enantio- and diastereoselective aziridination

The synthesis of enantioenriched aziridines is important for drug development due to their prevalence in bioactive molecules. Previous methods often use expensive catalysts, activated substrates, or show poor stereoselectivity. Herein, we report a novel organocatalytic approach using enantioenriched [2.2]paracyclophane (PCP)-based sulfenate anion catalysts, enabling the synthesis of 18 cyclopropanated aziridines from unactivated imines and commercially available benzyl chlorides in 50-99% yields with 73-99% ee and >20 : 1 dr. This approach fills a gap in the existing methods for aziridine synthesis, facilitating the generation of cyclopropyl-substituted aziridines with high stereoselectivity under mild and transition metal-free reaction conditions.