Li Zong-Jun, Li Shu-Hui, Sun Tao, Hou Hui-Lei, Gao Xiang
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, China.
J Org Chem. 2015 Apr 3;80(7):3566-71. doi: 10.1021/acs.joc.5b00253. Epub 2015 Mar 18.
Upon reduction, singly bonded 1,2,4,15-C60 dimers with an oxazoline or imidazoline heterocycle dissociate into monoanionic 1,2,4-C60 intermediates, which surprisingly leads to the formation of 1,2,3,16-C60 rather than 1,2,4,15-C60 adducts of the original configuration by further benzylation, even though the analogue of dibenzylated C60 oxazoline with a 1,2,4,15-configuration is stable and has been obtained. These results are corroborated by computational calculations, which rationalize the reaction and clarify the structure of the 1,2,3,16-C60 adducts, providing new insights into the intrinsic reactivity of singly bonded C60 dimers.
还原后，带有恶唑啉或咪唑啉杂环的单键1,2,4,15-C60二聚体解离成单阴离子1,2,4-C60中间体，令人惊讶的是，通过进一步苄基化，这导致形成1,2,3,16-C60加合物，而不是原始构型的1,2,4,15-C60加合物，尽管具有1,2,4,15-构型的二苄基化C60恶唑啉类似物是稳定的并且已经获得。这些结果得到了计算计算的证实，该计算使反应合理化并阐明了1,2,3,16-C60加合物的结构，为单键C60二聚体的内在反应性提供了新的见解。
