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2012 , Vol. 70 >Issue 10: 1201 - 1206

DOI: https://doi.org/10.6023/A1108182

研究论文

手性氨基醇诱导联苯构象转化制备轴手性联苯化合物

  • 王利敏 ,
  • 程森祥 ,
  • 陈彤 ,
  • 常俊标
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  • a 河南省科学院高新技术研究中心 郑州 450002;
    b 郑州大学化学系 郑州 450001

收稿日期: 2011-08-18

  修回日期: 2012-01-04

  网络出版日期: 2012-05-16

基金资助

国家杰出青年科学基金(No. 30825043)和国家自然科学基金(No. 20572017)资助项目.

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Preparation of Axially Chiral Biphenyls by Configuration Transformation Based on Chiral Amino Alcohols

  • Wang Limin ,
  • Cheng Senxiang ,
  • Chen Tong ,
  • Chang Junbiao
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  • a Hi-tech. Research Center, Henan Academy of Sciences, Zhengzhou 450002;
    b Department of Chemistry, Zhengzhou University, Zhengzhou 450001

Received date: 2011-08-18

  Revised date: 2012-01-04

  Online published: 2012-05-16

Supported by

Project supported by the National Outstanding Young Scholar Science Foundation of National Natural Science Foundatiion of China (No. 30825043) and the National Natural Science Foundation of China (No. 20572017).

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摘要

在(S)-氨基丙醇及(R)-氨基丙醇手性臂的作用下, (M/P)-4,4'-二甲氧基-5,6,5',6'-二次甲二氧基-2-甲酸酯-2'-甲酰氨联苯经构型转化, 制备了光学纯轴手性联苯化合物(P, S)-3a 和(M, R)-3a. 测定了(P, S)-3a 的晶体结构及CD 光谱. 结果表明, 化合物(P, S)-3a 晶体属单斜晶系, P2(1)空间群, 晶胞参数为a＝12.122(2) Å, b＝8.9911(18) Å, c＝12.779(3) Å, β＝112.38(3)°, 在晶体中存在两组分子间氢键相互作用, 一组氢键由羟基氢与另一分子酰胺基团的羰基氧组成O—H…O,另一组由酰胺基团的NH 与另一分子酰胺基团的羰基氧构成N—H…O, 每一分子通过四个氢键与另外两个分子相连,构成棒状结构. 由CD 光谱确定了(M, R)-3b 的立体构型. 此外, 由(P, S)-3a 合成了轴手性化合物(P)-2,2'-二羟甲基-4,4'-二甲氧基-5,6,5',6'-二亚甲二氧基-联苯(6a).

关键词： 轴手性联苯; 诱导结晶; 构型转化

本文引用格式

王利敏 , 程森祥 , 陈彤 , 常俊标 . 手性氨基醇诱导联苯构象转化制备轴手性联苯化合物[J]. 化学学报, 2012 , 70(10) : 1201 -1206 . DOI: 10.6023/A1108182

Abstract

Axially chiral biphenyls (P, S)-3a and (M, R)-3b were obtained from (M/P)-4,4'-dimethoxy- 5,6,5',6'-bis(methylenedioxy)-2-carboxylester-2'-carboxamide biphenyls via configuration transformation of the biphenyls with (S)-alaninol or (R)-alaninol chiral-arm. Crystal structure of (P, S)-3a was determined. The crystal of (P, S)-3a belongs to monoclinic, space group P2(1), a＝12.122(2) Å, b＝8.9911(18) Å, c＝ 12.779(3) Å, β＝112.38(3)°. There are two kinds of hydrogen-bonding in the (P, S)-3a crystal. The first is hydrogen-bonding between the hydroxyl group of the amino alcohol arm and the amide oxygen of a neighboring molecule. The second is hydrogen-bonding between the amide hydrogen atom and the amide oxygen of a neighboring molecule. Each molecule is linked to its two adjacent molecules by four intermolecular H-bonds. The configuration of (M, R)-3b was assigned based on the CD spectra. In addition, from (P, S)-3a, (P)-2,2'-dihydroxymethyl-4,4'-dimethoxy-5,6,5',6'-bis(methylenedioxy)-biphenyl (6a) was synthesized.

Key words： axially chiral biphenyl; crystallization induced; configuration transformation

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