Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
J Org Chem. 2011 Mar 18;76(6):1804-13. doi: 10.1021/jo102483x. Epub 2011 Feb 3.
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.
报道了氧和氮原子桥联的三角棱柱形双环芳烃的合成和功能化。通过片段偶联方法，使用 1,3,5-三(对羟苯基)苯和 2,4,6-三(对氨基苯基)三嗪作为基本单元，氯三嗪作为支柱，制备了富电子和缺电子芳环内部的分子三角棱柱体。氯三嗪部分与功能化胺的芳族亲核取代反应导致在边缘位置进行功能化的三角棱柱体，而使用 2,4,6-三[(对烯丙基氨基)苯基]三嗪衍生物作为起始原料，则可得到顶点氮位置上功能化的三角棱柱体。通过 X 射线晶体学揭示了在固态下对称和扭曲的分子三角棱柱体。然而，根据 NMR 光谱数据，所有合成的笼状分子在溶液相中很可能采用高度对称的三角棱柱结构。功能化的形状保持三角棱柱结构可能在分子识别以及超分子化学中构建更高更复杂的分子结构中找到应用。
