Synthesis of water-soluble cyclophane hexamers having a triphenylene core and their enhanced guest-binding behavior
Synthesis of water-soluble cyclophane hexamers having a triphenylene core and their enhanced guest-binding behavior
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具有苯并菲核心的水溶性环芳六聚体的合成及其增强的客体结合行为
DOI：
10.1021/acs.joc.6b00558
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
and S. Kusano
中科院分区：
文献类型：
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作者：
O. Hayashida;T. Matsuo;K. Nakamura;and S. Kusano
以三苯基-2,3,6,7,10,11-己二醇为核心，采用Williamson醚法合成四氮杂[6.1.6.1]副环烷衍生物，制备了水溶性环烷六聚体的前体化合物。通过去除前驱体上的保护基团，得到阳离子环烷六聚体(1)。荧光滴定实验证明，阳离子环烷六聚体1具有大环多价效应；与单体环烷相比，6-苯胺萘-2-磺酸盐和6-对甲苯胺萘-2-磺酸盐的主客体结合常数(K)分别提高了63倍和62倍。同样地，很容易由1制备的阴离子环烷六聚体2，与阳离子客体如阿霉素和柔红霉素的盐酸作为抗癌药物，表现出大环多价效应。
A key compound, a precursor of water-soluble cyclophane hexamer, was prepared via Williamson ether synthesis of tetraaza[6.1.6.1]paracyclophane derivatives bearing a bromoacetamide moiety with triphenylene-2,3,6,7,10,11-hexaol as a core. A cationic cyclophane hexamer (1) was obtained by removing the protecting groups from the precursor. Fluorescence titration experiments proved that cationic cyclophane hexamer1showed macrocyclic multivalency effects; i.e., 1:1 host/guest binding constants (K) of1with anionic guests, 6-anilinonaphthalene-2-sulfonate and 6-p-toluidinonaphthalene-2-sulfonate, were increased about 63- and 62-fold, respectively, relative to those of monomeric cyclophane. Similarly, anionic cyclophane hexamer2, which was easily prepared from1, showed macrocyclic multivalency effects inKvalues with cationic guests such as hydrochlorides of doxorubicin and daunorubicin as an anticancer drug.