Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
J Org Chem. 2013 Feb 1;78(3):1157-62. doi: 10.1021/jo3026302. Epub 2013 Jan 23.
Four isomers are currently known for the trioxygenated fullerene derivative C(60)(O)(3), three regioisomers with all of the oxygen addends as epoxy groups and the unstable ozonide isomer with a 1,2,3-trioxlane ring. Here we report the synthesis of an open-cage isomer for C(60)(O)(3) with a ketolactone moiety embedded into the fullerene skeleton through a three-step procedure mediated by fullerene peroxide chemistry. Two fullerene skeleton carbon-carbon bonds are cleaved in the process. The open-cage derivative C(60)(O)(3) can be converted back to C(60) through deoxygenation with PPh(3). Single crystal X-ray structure confirmed the open-cage structure.
目前已知四氧代富勒烯衍生物 C(60)(O)(3)有三种同分异构体，它们都有三个环氧基团作为加合物，以及不稳定的臭氧化物异构体，具有 1,2,3-三恶烷环。在这里，我们报告了一种通过富勒烯过氧化物化学介导的三步法合成的 C(60)(O)(3)的开笼异构体，其中一个酮内酯部分通过三个步骤嵌入富勒烯骨架中。在这个过程中，两个富勒烯骨架的碳-碳键被切断。开笼衍生物 C(60)(O)(3)可以通过三苯基膦(PPh(3))脱氧转化回 C(60)。单晶 X 射线结构证实了开笼结构。
