Journal of Organic Chemistry 2008-04-04

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

Xiaobing Yang, Shaohua Huang, Zhenshan Jia, Zuo Xiao, Zhongping Jiang, Qianyan Zhang, Liangbing Gan, Bo Zheng, Gu Yuan, Shiwei Zhang

Index: J. Org. Chem. 73(7) , 2518-26, (2008)

Full Text: HTML

Abstract

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.