SIOC English
化学学报
高级检索

化学学报 ›› 2006, Vol. 64 ›› Issue (14): 1465-1473. 上一篇    下一篇

研究论文

一种含有手性联萘“铰链”单元的环芳分子的设计、合成及表征

安德烈*，陈燕桂，张英俊，陈强，张志扬，严宏，孟桂英，赵文应，于正英   

  1. (湖南大学化学化工学院 长沙 410082)
  • 投稿日期:2005-12-22 修回日期:2006-03-28 发布日期:2006-07-28
  • 通讯作者: 安德烈

Design, Synthesis and Characterization of a New Type of Cyclo-phane Containing Chiral Binaphthyls as Hinges Units

AN De-Lie*, CHEN Yan-Gui, ZHANG Ying-Jun, CHEN Qiang, ZHANG Zhi-Yang, YAN Hong, MENG Gui-Ying, ZHAO Wen-Ying, YU Zheng-Ying   

  1. (College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082)
  • Received:2005-12-22 Revised:2006-03-28 Published:2006-07-28
  • Contact: AN De-Lie

PDF

1099

被引次数

13

基于联萘衍生物手性构型高度稳定以及联萘结构中2个萘平面的两面角可以在一定范围内张合的特点, 分别以光学活性的(R)和(S)-2,2'-二乙炔基-1,1'-联萘为模板, 设计了一种含有8个“铰链”结构单元的新的环芳分子¾—(R,R,R,R,R,R,R,R)-3和(S,S,S,S,S,S,S,S)-3. 其合成路线涉及间苯基连接桥的链接, 保护基的脱去和控制导入以及分子间偶合等步骤. 用MS, IR, UV-Vis, 1H和13C NMR以及元素分析等技术对中间体和目标化合物进行了结构表征. 测定并比较了2个目标化合物的比旋光度[α]D和圆二色(CD)性质. 在CH2Cl2溶液中, 两个异构体(R,R,R,R,R,R,R,R)-3和(S,S,S,S,S,S,S,S)-3的[α]D25值分别为－911.8和＋908.6, 并且它们的CD谱表现出对称的镜像特征．这些实验结果清楚地反映了它们之间的对映异构关系.

关键词: 光学活性, 联萘模板, 环芳化合物, 对映异构体, 合成

Based on highly stable chiral configuration of binaphthyls and behavior of extension/contraction of the dihedral angle between the two naphthalene rings in binaphthyl, we have designed two cyclophane enantiomers (R,R,R,R,R,R,R,R)-3 and (S,S,S,S,S,S,S,S)-3 containing eight chiral binaphthyl units by utilizing (R) and (S)-2,2'-diethynyl-1,1'-binaphthyl as hinges template, respectively. The synthetic procedure involved the multi steps reactions including the linking of meta-substituted benzene-bridge, removal and control introduction of protecting group, as well as intermolecular cross-coupling, etc. MS, IR, 1H and 13C NMR as well as elemental analysis characterized intermediates and target compound 3. The specific rotations ([α]D) of two isomers in CH2Cl2 are －911.8 and ＋908.6, and their circular dichroism (CD) spectra represented exactly mirror images of each other. These results reflected unambiguously enantiomeric relation between two optically pure isomers.

Key words: chirality, binaphthyl template, cyclophane, enantiomer, synthesis