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化学学报
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化学学报 ›› 2012, Vol. 70 ›› Issue (10): 1201-1206.DOI: 10.6023/A1108182 上一篇    下一篇

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a, 程森祥a, 陈彤a, 常俊标a,b   

  1. 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
  • 投稿日期:2011-08-18 修回日期:2012-01-04 发布日期:2012-05-16
  • 通讯作者: 常俊标 E-mail:leeme2011@yahoo.com.cn; changjunbiao@zzu.edu.cn
  • 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.

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

Wang Limina, Cheng Senxianga, Chen Tonga, Chang Junbiaoa,b   

  1. a Hi-tech. Research Center, Henan Academy of Sciences, Zhengzhou 450002;
    b Department of Chemistry, Zhengzhou University, Zhengzhou 450001
  • Received:2011-08-18 Revised:2012-01-04 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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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

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