高等学校化学学报

高等学校化学学报 ›› 1999, Vol. 20 ›› Issue (7): 1081.

• 论文 • 上一篇    下一篇

(R)-乙基-2-吡啶亚砜与(4R,5R)-TADDOL包结晶体[C7H9NOS·C31H30O4]的晶体结构分析

朱槿1, 周忠远1, 付芳敏1, 邓金根1, 宓爱巧1, 蒋耀忠1, 邱太源2   

  1. 1. 中国科学院成都有机化学研究所不对称合成联合开放实验室, 成都 610041;
    2. 中兴大学化学系, 台中 40227
  • 收稿日期:1998-07-23 出版日期:1999-07-24 发布日期:1999-07-24
  • 通讯作者: 蒋耀忠
  • 作者简介:朱槿,女,34岁,副研究员
  • 基金资助:

    国家自然科学基金(批准号:29790125)资助课题

Studies on Crystal Structure of Inclusion Chiral Crystal of (R)-Ethyl-2-pyridyl Sulfoxide with (4R,5R)-TADDOL

ZHU Jin1, ZHOU Zhong-Yuan1, FU Fang-Min1, DENG Jin-Geng1, MI Ai-Qiao1, JIANG Yao-Zhong1, QIU Tai-Yuan2   

  1. 1. Union Laboratory of Asymmetric Synthesis, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041;
    2. Department of Chemistry, Chung-Hsing University, Taichung, 40227
  • Received:1998-07-23 Online:1999-07-24 Published:1999-07-24

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摘要： (R)-乙基-2-吡啶亚砜与(4R,5R)-二(羟基-二苯基-甲基)-2,2-二甲基-1,3-二氧戊环(TAD-DOL)可以形成物质的量比为1:1的手性包结晶体,X射线衍射分析确定该晶体属单钭晶系,P21空间群,a=0.9701(2)nm,b=0.9953(2)nm,c=1.7392(2)nm;β=92.079°(14),V=1.6781(5)nm3,Z=2,Dc=1.230g/cm3,分子式C38H39NO5S,Mr=621.76,最终偏离因子R=0.0351,RW2=0.0772,Flack值为0.1(2).结构分析表明,主客体存在分子间氢键.光学纯的TADDOL与消旋的乙基吡啶亚砜(1)作用时,TADDOL对1具有很好的手性识别能力,选择性地与1的一个对映体形成氢键,长成晶体.参照晶体结构确定了1的两个对映体的绝对构型.

关键词: 手性亚砜, TADDOL, 包结晶体

Abstract: The synthesis and crystal structure of 1:1 inclusion chiral crystal formed from (R)-ethyl-2-pyridyl sulfoxide with (4R,5R)-α,α,α',α'-tetraaryl 1,3-dioxolane 4,5-dimethanol(TADDOL) were reported here. The crystal belongs to monoclinic, space group P21, a=0.9701(2) nm, b=0.9953(2) nm, c = 1.7392(2)nm; β=92.079°(14), V=1.6781(5)nm3, Mr= 621.76, Z=2, Dc= 1.230 g/cm3. The final refinement converges to R=0.0531 and Rw2= 0.0772 for 2335 observed independent reflections. Flack value is 0.1 (2). There is an intermolecular hydrogen bond in the inclusion crystal. Chiral TADDOL and ethyl-2-pyridyl sulfoxide(1) can be recognized each other in the inclusion crystal. Moreover, sulfoxide(1) in high enantiomeric excess was preparaed by resolution through inclusion complexation with the chiral TADDOL. The absolute configuration of (-)-ethyl-2-pyridyl sul-foxide was confirmed to be (R), which was assigned by the (R,R) absolute configuration of the TADDOL as an internal reference.

Key words: Chiral sulfoxide, TADDOL, Inclusion crystal

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