Hu Xiangqing, Jiang Zhongping, Jia Zhenshan, Huang Shaohua, Yang Xiaobing, Li Yuliang, Gan Liangbing, Zhang Shiwei, Zhu Daoben
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory Organic Solids, Chinese Academy of Science, Institute Chemistry, Beijing, 100080, China.
Chemistry. 2007;13(4):1129-41. doi: 10.1002/chem.200600932.
Ammonia and aliphatic amines react readily in the oxygen-rich regions of the Cs symmetric fullerene peroxides C60(O)(OOtBu)4 (1) and C60(OH)(Br)(OOtBu)4 (2 c). Michael addition-type hydroamination of the 1,4-diene moiety on the central skew-pentagon was observed when 1 was treated with ammonia or with nonbulky primary amines, while sterically demanding primary amines opened the epoxy moiety to form vicinal aminohydroxy fullerene compounds with the amino group on the central pentagon. In 2 c the bromo group was replaced under similar conditions by ammonia and primary amines. Cyclic secondary amines showed different reaction patterns, forming hydrogenation products or aminoketal-fullerenes when treated with 1 and 2 c, respectively. Single-electron transfer (SET) is the key step in all the proposed mechanisms. The compounds were characterized by their spectroscopic data, and in addition, three single-crystal X-ray structures were obtained.
氨和脂肪族胺在Cs对称富勒烯过氧化物C60(O)(OOtBu)4 (1)和C60(OH)(Br)(OOtBu)4 (2 c)的富氧区域容易发生反应. 用氨或体积较小的伯胺处理1时，观察到中心偏斜五边形上的1,4-二烯部分发生迈克尔加成型氢胺化反应，而空间位阻较大的伯胺会打开环氧部分以形成中心五边形上带有氨基的邻氨基羟基富勒烯化合物。在类似条件下，2 c中的溴基团会被氨和伯胺取代。环状仲胺表现出不同的反应模式，分别用1和2 c处理时会形成氢化产物或氨基缩酮-富勒烯。单电子转移(SET)是所有提出的反应机理中的关键步骤。通过光谱数据对这些化合物进行了表征，此外，还获得了三种单晶X射线结构。
