Design of Macrocyclic Multidentates Discriminating Molecular Chirality and Their Recognition Abilities

本研究发展了一种简便的含活性羟基的C_2-对称手性冠醚的合成方法，并考察了由该中间体衍生的几种C_2-对称手性冠醚衍生物对伯铵盐的手性识别能力。研究结果如下：1.作为开发基于冠醚骨架的手性识别主体分子的预备性研究，通过使用几种类型的双臂丙醚来考察侧臂在与客体阳离子络合中的参与。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.提出了一种新的合成方法，合成了具有多个活性官能团的（S，S）-2，12-双（羟甲基）-2，12-二甲基-18-冠-6.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、苯氧基甲基、苄氧基甲基、烯丙氧基甲基和乙酰氧基甲基等几种侧臂。用~ 1H-NMR滴定法测定了冠醚衍生物对α-（1-萘基）乙胺、α-苯乙胺和苯甘氨醇高氯酸盐的手性识别能力，发现侧臂对手性识别有积极的参与.

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.