An unprecedented [5,6]-open adduct via a direct benzyne-C₆₀ cycloaddition

详细信息    查看全文

• 作者：Gyoungsik Kim ; Kyu Cheol Lee ; Jonggi Kim ; Jungho Lee ; Sang Myeon Lee ; Jeong Chul Lee ; Jung Hwa Seo ; Won-Youl Choi ; Changduk Yang
• 关键词：Buckminsterfullerene ; Benzyne ; [5 ; 6]-Open adduct ; [6 ; 6]-Closed adduct ; Cycloaddition
• 刊名：Tetrahedron
• 出版年：2013
• 出版时间：2 September, 2013
• 年：2013
• 卷：69
• 期：35
• 页码：7354-7359
• 全文大小：973 K

文摘

Cycloaddition is one of the best-studied types of reactions in the organic chemistry of fullerenes, engendering [6,6]-closed adducts in the vast majority of cases. Notwithstanding that a formation of open fulleroid structures is undoubtedly of theoretical interest, no one has demonstrated the conformation of [5,6]-open fulleroid via the direct cycloadditions. Here, we establish that cycloaddition between C₆₀ and benzyne in situ generated from 2-amino-4,5-dibutoxybenzoic acid affords a new type of elusive [5,6]-open structure that is characterized on the basis of NMR, UV-vis spectroscopy, and cyclic voltammetry. Additionally, from density functional theory (DFT) calculations for possible [5,6]-open and [6,6]-closed adducts induced of benzyne-C₆₀ reaction, as expected, features such as the charge distributions, binding characteristics, and frontier molecular orbital levels, are affected by the different binding modes in C₆₀ cage.