Reactivity of Fullerene Epoxide: Preparation of Fullerene-Fused Thiirane, Tetrahydrothiazolidin-2-one, and 1,3-Dioxolane

The epoxide moiety in the fullerene-mixed peroxide C60(O)(OOtBu)4 1 reacts readily with aryl isocyanates ArNCS (Ar = Ph, Naph) to form both the thiirane derivative C60(S)(OOtBu)4 and fullerene-fused tetrahydrothiazolidin-2-one. The reaction of 1 with trimethylsilyl isothiocyanate TMSNCS yields the isothiocyanate derivative C60(NCS)(OH)(OOtBu)4, the isothiocyanate and hydroxyl moieties of which could be converted to a fullerene-fused tetrahydrothiazolidin-2-one ring with alumina quantitatively. Treating 1 with BF3·Et2O yields the fullerene-fused [1,3,2]-dioxoborolane derivative C60(O2BOH)(OOtBu)4. In the presence of aldehyde or acetone, BF3·Et2O catalyzes the conversion of epoxide to fullerene-fused 1,3-dioxolane derivatives. The products are characterized by spectroscopic data. Two of the compounds are also characterized by single-crystal X-ray analysis.