Highly Regioselective Synthesis of Bis‐Aziridino[60]fullerene with Sulfilimine

In the course of our study of the development of a synthetic methodology for the aziridination of fullerenes, we recently reported the photochemical [2+1] cycloaddition reaction of nitrene onto C 60 generated from sulfilimine. Sulfilimines with an electron‐donating group on the N atom are well known to undergo Michael‐type reactions, followed by concomitant elimination of sulfide to afford the corresponding aziridines. In these reactions, sulfilimines act as a nucleophile to the electrophilic olefins. Furthermore, C 60 has characteristic features of a low LUMO level and electron‐accepting properties. Therefore, it can be an electrophilic olefin. In this context, sulfilimines might react with C 60 to afford the corresponding aziridinofullerenes. We have studied the thermal reaction of ( S,S )‐diphenylsulfilimines with C 60 and regioselectively synthesized bis‐ and tris‐aziridinated fullerenes. These structures were determined through spectroscopic analyses. Among these, the structure of bis‐aziridinated[60]fullerene, C 60 (NCH 3 ) 2 , was determined using single‐crystal X‐ray analysis. Results show that the multi‐aziridination occurs exclusively at the same six‐membered ring of C 60 to afford one isomer of the bis‐adduct and tris‐adduct.