Design of Macrocyclic Multidentates Discriminating Molecular Chirality and Their Recognition Abilities

大环多齿识别分子手性的设计及其识别能力

• 批准号: 13650903
• 负责人: NAKATSUJI Yohji
• 金额: $ 2.3万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650903/
• 关键词: Molecular Recognition; Chiral Crown Ether; Complexation; クラウンエーテル; キラル認識; リパーゼ触媒反応; C_2-対称

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.

在本研究中，我们开发了一种具有反应性羟基的C_2-对称手性冠醚的便捷合成方法，并检测了由关键中间体衍生的几种C_2-对称冠醚衍生物对伯铵盐的手性辨别能力，结果总结如下。如下： 1.作为基于冠醚支架的手性识别主体分子的制备研究，通过以下方法检查了侧臂在与客体阳离子的络合中的参与：结果发现，在冠环上引入供电子侧臂对于提高对碱金属和碱土金属阳离子的络合能力非常有效。 2．开发了具有多个反应性官能团的(S,S)-2,12-双(羟甲基)-2,12-二甲基-18-冠-6的合成方法。 3．通过(R,R)-2, 12双(羟甲甲基)-2, 12-二甲基-18-的羟基修饰，将萘氧基甲基、苯氧基甲基、苄氧基甲基、烯丙氧基甲基、乙酰氧基甲基等引入到18冠6环上。所得冠醚衍生物对高氯酸盐的(R)和(S)的手性识别能力。通过1H-NMR滴定法估算了α-(1-萘基)乙胺、α-苯基乙胺和苯基甘氨醇的手性识别，并观察到侧臂对手性识别的积极参与。

项目成果

Nakahara, Yoshio: "Fluorometric Sensing of Alkaline Earth Metal Cations by New Lariat Ethers Having Plural Pyrenylmethyl Groups on the Electron-donating Sidearms"Organic Letters. 4・16. 2641-2644 (2002)

Nakahara, Yoshio：“在给电子侧臂上具有多个芘基甲基的新型套索醚对碱土金属阳离子的荧光传感”有机快报 4・16 (2002)。

Yoshio Nakahara, Yasuo Matsumi, Wanbin Zhang, Toshiyuki Kida, Yohji Nakatsuji, and Isao Ikeda: "Fluorometric Sensing of Alkaline Earth Metal Cations by New Lariat Ethers Having Plural Pyrenylmettjyl Groups on the Electron-donating Sidearms"Org. Lett. 4 (1

Yoshio Nakahara、Yasuo Matsumi、Wanbin Zhang、Toshiyuki Kida、Yohji Nakatsuji 和 Isao Ikeda：“在电子供给侧臂上具有多个 Pyrenylmettjyl 基团的新型套索醚对碱土金属阳离子的荧光传感”Org。

Yohji Nakatsuji, Masahiro Muraoka, Hiroyuki Kajiya, Wanbin Zhang, Toshiyuki Kida, and Isao Ikeda: "Synthesis and Complexation Ability of a C-Pivot Type of Double-armed 15-Crown-5 Ethers toward Alkali Metal Cations"Bull. Chem. Soc. Jpn.. 75 (8). 1765-1770

Yohji Nakatsuji、Masahiro Muraoka、Hiroyuki Kajiya、Wanbin 张、Toshiyuki Kida 和 Isao Ikeda：“C-Pivot 型双臂 15-Crown-5 醚对碱金属阳离子的合成和络合能力”公牛。

Nakatsuji, Yohji: "Synthesis and Complexation Ability of a C-Pivot Type of Double-armed 15-Crown-5 Ethers toward Alkali Metal Cations"Bulletin of the Chemical Society of Japan. 75・8. 1765-1770 (2002)

Nakatsuji, Yohji：“双臂 15-冠-5 醚对碱金属阳离子的合成和络合能力”日本化学会通报 75・8（2002 年）。