Preparation of a 12-Membered Open-Cage Fullerendione through Silane/Borane-Promoted Formation of Ketal Moieties and Oxidation of a Vicinal Fullerendiol

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• 作者：Gang Zhang ; Qianyan Zhang ; Zhenshan Jia ; Sisi Liang ; Liangbing Gan ; Yuliang Li
• 刊名：Journal of Organic Chemistry
• 出版年：2011
• 出版时间：August 19, 2011
• 年：2011
• 卷：76
• 期：16
• 页码：6743-6748
• 全文大小：864K
• 年卷期：v.76,no.16(August 19, 2011)
• ISSN：1520-6904

文摘

[60]Fullerene mixed peroxide C₆₀ (OH)(Cl)(OOtBu) reacts with PhMe₂SiH/B(C₆F₅)₃ to give oxahomofullerene. Mechanistic investigation indicates that the hydroxyl group in the central pentagon ring is essential to convert the tert-butylperoxo group into a ketal moiety. Migration of the silyl group and transformation of the siloxy group into a phenyl group are observed in the deprotection of the fullerene bound siloxy group. A 12-membered open-cage fullerendione was obtained through oxidation of a [6,6]-fullerendiol. This orifice could be closed to form ketal/hemiketal moieties by BF₃-catalyzed reaction with methanol. All of the new fullerene derivatives were characterized by spectroscopic data, and structure of the open-cage fullerendione was also confirmed by single-crystal X-ray analysis.