Design of Macrocyclic Multidentates Discriminating Molecular Chirality and Their Recognition Abilities

在本研究中，我们开发了一种简便的具有反应性羟基的C_2-对称性冠醚的合成方法，并考察了关键中间体衍生的几种C_2-对称性冠醚衍生物对伯铵盐的手性识别能力。研究结果总结如下：1.研究成果。作为开发基于冠醚支架的手性识别主体分子的预备性研究，以几种类型的双臂套索为例，考察了侧臂参与与客体阳离子的络合反应。结果表明，在冠环上引入给电子侧臂可以有效地提高碱金属和碱土金属阳离子的络合能力。开发了一种具有多种活性官能团的(S，S)-2，12-二羟甲基-2，12-二甲基-18-冠-6的简便合成新工艺。通过对(R，R)-2，12-二(羟甲基)-2，12-二甲基-18-冠-6的羟基修饰，在18-冠-6环上引入了几种侧链，如萘氧甲基、苯氧甲基、苄氧甲基、烯丙氧甲基和乙酰氧甲基。用1H-核磁共振滴定方法评价了所合成的冠醚衍生物对α-(1-萘基)乙胺、α-苯乙胺和苯甘氨酚的高氯酸盐(R)和(S)的手性识别能力，并观察到侧臂在手性识别中的正向参与。

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.