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Progress in Chemistry 2006, Vol. 18 Issue (05): 533-541 Previous Articles   Next Articles

• Review •

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: Revised: Online: Published:
  • Contact: Linhui Tong
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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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