Preparation of [5,6]- and [6,6]-oxahomofullerene derivatives and their interconversion by Lewis acid assisted reactions of fullerene mixed peroxides.
[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 (oxohomo[60]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.
Huang
Shaohua
S
Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, Peking University, Beijing 100871, China.
Xiao
Zuo
Z
Wang
Fudong
F
Zhou
Jiang
J
Yuan
Gu
G
Zhang
Shiwei
S
Chen
Zhongfang
Z
Thiel
Walter
W
von Ragué Schleyer
Paul
P
Zhang
Xiang
X
Hu
Xiangqing
X
Chen
Bichu
B
Gan
Liangbing
L