Preparation of [5,6]- and [6,6]-oxahomofullerene derivatives and their interconversion by Lewis acid assisted reactions of fullerene mixed peroxides |
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Authors: | Huang Shaohua Xiao Zuo Wang Fudong Zhou Jiang Yuan Gu Zhang Shiwei Chen Zhongfang Thiel Walter von Ragué Schleyer Paul Zhang Xiang Hu Xiangqing Chen Bichu Gan Liangbing |
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Institution: | Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Peking University, Beijing 100871, China. |
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Abstract: | 60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both 5,6]- and 6,6]-fullerene hemiketals (oxohomo60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. |
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Keywords: | epoxides fullerenes hemiketals isomerization peroxides |
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