Synthesis and Functionalization of Heteroatom-Bridged Bicyclocalixaromatics, Large Molecular Triangular Prisms with Electron-Rich and -Deficient Aromatic Interiors
Synthesis and Functionalization of Heteroatom-Bridged Bicyclocalixaromatics, Large Molecular Triangular Prisms with Electron-Rich and -Deficient Aromatic Interiors
复制标题
具有富电子和缺芳香族内部的杂原子桥双环杯芳香族化合物、大分子三角棱柱的合成和功能化
DOI：
10.1021/jo102483x
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发表时间：
2011-03-18
影响因子：
3.6
通讯作者：
Wang, Mei-Xiang
中科院分区：
文献类型：
--
作者：
Naseer, Muhammad Moazzam;Wang, De-Xian;Wang, Mei-Xiang
报道了氧氮原子桥联的三棱柱结构双环芳环化合物的合成及功能化。以1，3，5-三（对羟基苯基）苯和2，4，6-三（对氨基苯基）三嗪为基本单元，氯代三嗪为柱，采用片段偶联法制备了富电子和缺电子芳香族分子三角柱.氯三嗪部分与官能化胺发生芳族亲核取代反应，得到了周边位置官能化的三角棱镜，而以2，4，6-三[（对烯丙基氨基）苯基]三嗪衍生物为原料，得到了顶点氮位置官能化的三角棱镜。用X射线晶体学方法研究了固体状态下的对称和畸变的分子三角柱。然而，由NMR光谱数据证明，所合成的笼状分子在溶液相中最可能采用高度对称的三棱柱结构。功能化的形状保持的三棱柱结构可能在超分子化学中的分子识别和更高和更复杂的分子结构的构建中找到应用。
The synthesis and functionalization of oxygen and nitrogen atom bridged bicyclocalixaromatics of triangular prism structures are reported. By means of a fragment coupling approach, molecular triangular prisms of electron-rich and electron-deficient aromatic interiors were prepared using 1,3 5-tri(p-hydroxyphenyl)benzene and 2,4,6-tri(p-aminophenyl)triazine as base units and chlorotriazines as pillars. Aromatic nucleophilic substitution reaction of chlorotriazine moieties with functionalized amines led to triangular prisms with functionalizations on the peripheral edge positions, while functionalized triangular prisms on the vertex nitrogen positions were obtained using 2,4,6-tri[(p-allylamino)phenyl]triazine derivative as a starting material. Symmetrical and distorted molecular triangular prisms in the solid state were revealed by X-ray crystallography. As evidenced by NMR spectroscopic data, however, all cage molecules synthesized most probably adopted highly symmetric triangular prism structures in solution phase. The functionalized shape-persistent triangular prism structures might find applications in molecular recognition and in the construction of higher and more sophisticated molecular architectures in supramolecular chemistry.