(Invited) Unprecedented Aromatic Ring Scissoring Observed in the Reaction of Sc3n@Ih -C80 with Aryl Azides

Abstract

A number of reactions of endohedral metallofullerenes (EMFs) have been reported in the literature. Recently, we investigated the reaction of aryl azides with Sc3N@Ih -C80. It was found that isomeric [5,6]- and [6,6]-azafulleroids can be obtained from the thermal reaction of Sc3N@Ih -C80 with 4-isopropoxyphenyl azide, while photoirradiation leads exclusively to the [6,6]-azafulleroid.[1] Surprisingly, when the thermal reaction was conducted at a lower temperature and under the aerobic conditions, an EMF isoxazoline derivativehaving a hexa-2,4-dienal moiety was obtained. This unprecedented reaction involved the aromatic ring scissoring and participation of O2. The same phenomena were applied to the reaction of Sc3N@Ih -C80 with other electro-rich aryl azides.