Cage‐Opened C <sub>60</sub> Isomers with Different Reactivities
Cage‐Opened C <sub>60</sub> Isomers with Different Reactivities
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具有不同反应活性的开笼 C <sub>60</sub> 异构体
DOI：
10.1002/ajoc.202100676
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发表时间：
2022
影响因子：
2.7
通讯作者：
Murata Yasujiro
中科院分区：
文献类型：
--
作者：
Zhang Sheng;Hashikawa Yoshifumi;Murata Yasujiro
我们合成了两个开笼的C60异构体，它们的孔上有不同排列的亚胺基团，并考察了它们对亲核试剂的反应活性。两种异构体都通过与N-甲基吗啉N-氧化物的反应以相似的产率扩大了开度，而与甲醇的反应通过跨环环合引起了孔口收缩，导致了明显不同的产率。后一种反应产物的骨架上有一个新的六角环或七角环。观察到的反应活性差异可以解释为含有六边形的异构体比其他异构体具有更大的热力学稳定性。
We synthesized two cage‐opened C60isomers with different arrangement of an imine moiety on their orifices and investigated reactivities of them toward nucleophiles. Both isomers underwent the enlargement of the opening by the reaction withN‐methylmorpholineN‐oxide in comparable yields while the reaction with MeOH caused an orifice contraction via a transannular cyclization resulting in obviously different yields. The products in the latter reaction have a new hexagonal or heptagonal ring on their skeletons. The observed difference in reactivity could be explained by the greater thermodynamic stabilization in the hexagon‐containing isomer compared with the other.