Cyclodextrin-Based Size-Complementary [3] Rotaxanes: Selective Synthesis and Specific Dissociation
Cyclodextrin-Based Size-Complementary [3] Rotaxanes: Selective Synthesis and Specific Dissociation
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DOI：
10.1002/chem.201405005
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发表时间：
2014-12-15
影响因子：
4.3
通讯作者：
Takata, Toshikazu
中科院分区：
文献类型：
--
作者：
Akae, Yosuke;Koyama, Yasuhito;Takata, Toshikazu
以α -环糊精（CD）为基础，与异氰酸芳酯在水中进行端盖反应，在一锅中制备了具有烷基烯轴的尺寸互补[3]轮烷。x射线结构分析表明[3]轮烷的选择性形成具有头对头的规律性。带适当端基的[3]轮烷通过逐步解离进行热降解，不仅可以得到原始组分，还可以得到[2]轮烷。从动力学曲线上可以估计出[2]轮烷的最高收率为94%。热力学研究和noesi分析表明[3]轮烷具有特殊的稳定性，[3]轮烷对组分的解离能力可以通过控制端基的结构、CD基的方向和烷基轴的长度来调节。
alpha-Cyclodextrin (CD)-based size-complementary [3] rotaxanes with alkylene axles were prepared in one-pot by end-capping reactions with aryl isocyanates in water. The selective formation of [3] rotaxane with a head-to-head regularity was indicated by the X-ray structural analyses. Thermal degradation of the [3] rotaxanes bearing appropriate end groups proceeded by stepwise dissociation to yield not only the original components but also [2] rotaxanes. From the kinetic profiles of the deslippage, it turned out that the maximum yield of [2] rotaxane was estimated to be 94 %. Thermodynamic studies and NOESY analyses of such rotaxanes revealed that [2] rotaxanes are specially stabilized, and that the dissociation capability of the [3] rotaxanes to the components can be adjusted by controlling the structure of the end groups, direction of the CD groups, and length of the alkylene axle.