Design of Macrocyclic Multidentates Discriminating Molecular Chirality and Their Recognition Abilities

在本研究中，我们开发了一种具有活性羟基的c_2对称手性冠醚的简便合成方法，并测试了几个由关键中间体衍生的c_2对称冠醚衍生物对伯铵盐的手性识别能力。结果总结如下：1。作为开发基于冠醚支架的手性识别宿主分子的准备研究，用几种类型的双臂支醚考察了侧臂参与客体阳离子络合的情况。结果表明，在冠环上引入给电子侧臂可以有效地提高对碱金属和碱土金属阳离子的络合能力。建立了具有复数反应官能团的（S， S）- 2,12 -双（羟甲基）- 2,12 -二甲基-18-冠-6的简便合成方法。通过对（R， R）- 2,12双（羟甲基）- 2,12 -二甲基-18-冠-6的羟基进行修饰，在18冠-6环上引入了萘氧基甲基、苯基氧基甲基、苯氧基甲基、烯丙基氧基甲基和乙酰氧基甲基等几种侧链。用1H-NMR滴定法测定了冠醚衍生物对高氯酸盐α-（1-萘基）乙胺、α-苯乙胺和苯甘二醇(R)和(S)的手性识别能力，并观察到侧臂积极参与手性识别。

In this study, we developed a convenient synthetic procedure for C_2-symmetirc chiral crown ether having reactive hydroxyl groups and examined the chiral discrimination ability of the several C_2-symmetirc crown ether derivatives derived from the key intermediate toward primary ammonium salts. The results are summarized as follows.1. As a preparative study for the development of chiral recognition host molecules based on the crown ether scaffold, the participation of the sidearm in the complexation with guest cations was examined by using several type of double armed lariat ethers. As a result, the introduction of the electron-donating sidearm to the crown ring was found to be highly effective in increasing the complexation ability toward alkali metal and alkaline earth metal cations.2. A new convenient synthetic procedure for (S, S)-2, 12-bis(hydroxymethyl)-2, 12-dimethyl-18-crown-6 possessing plural reactive functional groups was developed.3. Several types of sidearms such as naphthyloxymethyl, phenyloxymethyl, benzyloxymethyl, allyloxymethyl, and acectyloxymethyl were introduced to the 18 crown-6 ring by modification of the hydroxyl groups of (R, R)-2, 12 bis(hydroxymemyl)-2, 12-dimethyl-18-crown-6. The chiral recognition ability of the resulting crown ether derivatives toward (R) and (S) of the perchlorate salts of α-(1-naphtyl) ethylamine, α-phenylethylamine, and phenylglycinol was estimated by 1H-NMR titration method and the positive participation of the sidearm in the chiral recognition was observed.