Reactivity of fullerene epoxide: Preparation of fullerene-fused thiirane, tetrahydrothiazolidin-2-one, and 1,3-dioxolane

Abstract

The epoxide moiety in the fullerene-mixed peroxide C(60)(O)(OO(t)Bu)(4) 1 reacts readily with aryl isocyanates ArNCS (Ar = Ph, Naph) to form both the thiirane derivative C(60)(S)(OO(t)Bu)(4) and fullerene-fused tetrahydrothiazolidin-2-one. The reaction of 1 with trimethylsilyl isothiocyanate TMSNCS yields the isothiocyanate derivative C(60)(NCS)(OH)(OO(t)Bu)(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 BF(3)center dot Et(2)O yields the fullerene-fused [1,3,2]-dioxoborolane derivative C(60)(O(2)BOH)(OO(t)Bu)(4). In the presence of aldehyde or acetone, BF(3)center dot Et(2)O 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.