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化学进展 2006, Vol. 18 Issue (05): 533-541 前一篇   后一篇

• 综述与评论 •

天然和修饰环糊精的不对称光化学

童林荟 鲁润华 井上佳久   

  1. 中国科学院兰州化学物理研究所 中国科学院成都生物所 大阪大学工学部分子化学系
  • 收稿日期:2005-11-01 修回日期:1900-01-01 出版日期:2006-01-01 发布日期:2006-01-01
  • 通讯作者: 童林荟
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导出 被引次数 ( 25 | 3 )

Asymmetric Photochemistry with Native and Modified Cyclodextrins

Linhui Tong Runhua Lu Yoshihisa Inoue Inoue   

  1. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences Chengdu Institute of Biology, Chinese Academy of Sciences Department of Molecular Chemistry, Faculty of Engineering, Osaka University
  • Received:2005-11-01 Revised:1900-01-01 Online:2006-01-01 Published:2006-01-01
  • Contact: Linhui Tong
用修饰的α-，β-，γ-环糊精(CDs)的包结增感作用研究(Z)-环辛烯(1Z)向手性(E)-异构体(1E)的超分子对映差向光异构反应。建立定量圆二色(CD)和差圆二色(DCD)公式, 研究修饰α-，β-，γ-环糊精衍生物与1Z包结反应的构象、化学量和稳定常数。 实验发现结合诱导的CD光谱变化是温度和修饰环糊精浓度的临界函数。同时发现光稳态E/Z随照射时间增长而增加最后达到光稳定状态, 但明显依赖于增感剂结构和溶液中甲醇含量，它与环糊精手性空腔被客体1Z占有率有直接关系。考查含o-,m-,p-羧酸甲酯基团的苯甲酸β-环糊精酯衍生物的光增感和对映差向能力，更好地认识到在CDs空腔内的有效光能转换是怎样发生的。用邻苯二甲酸β-环糊精酯的对映体过剩（ee）从2.9% 增加到24%。有趣的是产物的ee值与取代基常数（Hammett,σ）间没有明显的关系，却与某些苯甲酸β-CD酯的主体占有率有直接关系，即是通过分析在不同甲醇含量的水溶液中被一些β-CD衍生物增感的对映差向光异构反应中的ee，得出被底物1Z占有主体空腔的百分率 。
关键词： 修饰环糊精, 超分子光化学, 不对称合成, 对映差向光异构反应, 光增感作用
Supramolecular enantiodifferentiating photoisomerization of (Z)-cyclooctene(1Z) to chiral (E)-isomer(1E) has been studied via inclusion and sensitization by modified α-，β-，γ-cyclodextrins(CDs). Quantitative circular dichroism(CD) and differential circular dichroism(DCD) formula are established for studing the conformation, stoichiometry and stability constant of the complexation of 1Z with the modifiedα-,β-, and γ-cyclodextrin derivatives. We found experimentally that the CD spectral change induced upon complexation is a critical function of temperature and concentration of modified β-cyclodextrin. In addition, it is found that the photostationary-state E/Zincreases with increasing irradiation time to reach a photostationary state, but significantly depends on the sensitizer structure and the methanol content in solution,which is directly related to the occupancy of the CD's chiral cavity by guest 1Z. Photosensitizing and enantiodifferentiating abilities of the β-CD-benzoate derivatives,possessing o-,m-,p-mehoxycarbonyl group, are examined to better understand how the effective photoenergy transfer occurs inside the CDs cavity, and the enantiomeric excess (ee) is enhanced from 2.9% to 24% by using the β-CD-phthalate. Interestingly, the product's eeobtained did not show a clear relationship with the substituent's constant (Hammett's σ),it is found to be directly related to the host occupancy for some β-CD-benzoate, i.e. the percentage of host cavity occupied by the substrate 1Z through the analyses of the ee obtained upon the enantiodifferentiating photoisomerization sensitized by several β-CD derivatives in aqueous solutions of varying methanol contents.
Key words: modified cyclodextrins, supramolecular photochemistry, asymmetric synthesis, enantiodifferentiating photoisomerization, photosensitization

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