Palladium-Catalyzed Cyclization: Regioselectivity and Structure of Arene-Fused C60 Derivatives
Palladium-Catalyzed Cyclization: Regioselectivity and Structure of Arene-Fused C60 Derivatives
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DOI：
10.1021/jacs.7b09459
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发表时间：
2017-11-15
影响因子：
15
通讯作者：
Murata, Yasujiro
中科院分区：
文献类型：
--
作者：
Hashikawa, Yoshifumi;Murata, Michihisa;Murata, Yasujiro
用几种芳基卤化物和C-60在富勒烯C-60笼上进行了钯催化的环化反应。戊酸的加入加速了该反应，基于协同金属-去质子化机理的计算研究可以合理地解释这一现象。我们还使用具有相同亚结构的预功能化设计分子在C-60笼上展示了区域选择性pi功能化。单晶x射线分析和静电势图表明，由于萘融合和开口的构建，在C-60衍生物中包裹水的取向是静电要求的。
The palladium-catalyzed cyclization on the fullerene C-60 cage has been achieved using several aryl halides and C-60. This reaction was found to be accelerated by the addition of pivalic acid, which can be rationally explained by the computational study based on the concerted metalation-deprotonation mechanism. We also demonstrated the regioselective pi-functionalization using prefunctionalized designed molecules possessing the same substructure on the C-60 cage. The single crystal X-ray analysis and electrostatic potential map revealed that the orientation of entrapped H2O inside the naphthalene-fused open-cage C-60 derivative is electrostatically demanded due to the naphthalene-fusion and construction of the opening.