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Supramolecular Photochirogenesis with Novel Cyclic Tetrasaccharide: Enantiodifferentiating Photoisomerization of (Z)-Cyclooctene with Cyclic Nigerosylnigerose-Based Sensitizers

  1. Cheng Yang1,2,*,
  2. Wenting Liang2,
  3. Masaki Nishijima3,
  4. Gaku Fukuhara2,
  5. Tadashi Mori2,
  6. Hiroyuki Hiramatsu4,
  7. Yasufumi Dan-oh4,
  8. Kazuo Tsujimoto4,
  9. Yoshihisa Inoue2,*

Article first published online: 28 APR 2012

DOI: 10.1002/chir.22014

Issue

Chirality

Chirality

Special Issue: Proceedings from the 23rd International Symposium on Chirality, Liverpool, UK, 2011

Volume 24, Issue 11, pages 921–927, November 2012

Additional Information

How to Cite

Yang C., Liang W., Nishijima M., Fukuhara G., Mori T., Hiramatsu H., Dan-oh Y., Tsujimoto K. and Inoue Y. (2012), Supramolecular Photochirogenesis with Novel Cyclic Tetrasaccharide: Enantiodifferentiating Photoisomerization of (Z)-Cyclooctene with Cyclic Nigerosylnigerose-Based Sensitizers, Chirality. DOI: 10.1002/chir.22014

Author Information

  1. 1

    Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Saitama, Japan

  2. 2

    Department of Applied Chemistry, Osaka University, Suita, Japan

  3. 3

    Office for University-Industry Collaboration, Osaka University, Suita, Japan

  4. 4

    Hayashibara Co., Ltd., Okayama, Japan

*Y. Inoue, Department of Applied Chemistry, Osaka University, Yamada-oka, Suita 565-0871, Japan. E-mail: inoue@chem.eng.osaka-u.ac.jp; C. Yang, Department of Applied Chemistry, Osaka University, Yamada-oka, Suita 565-0871, Japan. E-mail: c.yang@chem.eng.osaka-u.ac.jp

Publication History

  1. Issue published online: 23 OCT 2012
  2. Article first published online: 28 APR 2012
  3. Manuscript Accepted: 12 JAN 2012
  4. Manuscript Received: 22 OCT 2011

Funded by

  • Japan Science and Technology Agency (CY and YI)
  • Japan Society for the Promotion of Science (GF, TM, and YI)
  • Sumitomo Foundation (CY and TM)
  • Iwatani Naoji Foundation (GF)
  • Mitsubishi Chemical Corporation Fund (TM)

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Keywords:

  • chiral photochemistry;
  • enantiodifferentiating photoisomerization;
  • planar chirality;
  • cyclooctene;
  • cyclic nigerosylnigerose;
  • supramolecular chemistry

ABSTRACT

Isophthalic and terephthalic acid monoesters of cyclic nigerosyl-(1→6)-nigerose (CNN), a cyclic tetrasaccharide composed of four d-glucopyranosyl residues connected by alternating α-1,3- and α-1,6-linkages, were synthesized as novel chiral supramolecular sensitizers for enantiodifferentiating photoisomerization of (Z)-cyclooctene (1Z) to planar chiral (E)-isomer (1E). Despite the saucer-shaped shallow cavity of CNN that does not immediately guarantee strong ground-state interactions with 1Z, the sensitizer-appended CNNs afforded optically active 1E in such enantiomeric excesses that are much improved than those obtained with an α-cyclodextrin analog and comparable with those obtained with a β-cyclodextrin analog. Interestingly, the enantiomeric excess values obtained were a critical function of temperature and solvent to show an inversion of the product chirality by changing the environmental variants. Nevertheless, all of the differential activation parameters calculated from the temperature-dependent enantiomeric excesses gave an excellent compensatory enthalpy–entropy relationship, indicating an operation of a single enantiodifferentiating mechanism in the present chiral photosensitization with modified CNNs. Chirality 24:921–927, 2012. © 2012 Wiley Periodicals, Inc.

Featured Compounds

Compound 1Z
Molecular Weight:110.1968
Molecular Formula:C8H14
InChIKey:URYYVOIYTNXXBN-UPHRSURJSA-N
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Compound R-(-)-1E
Molecular Weight:110.1968
Molecular Formula:C8H14
InChIKey:URYYVOIYTNXXBN-OWOJBTEDSA-N
View compound in article | Full details | Search this compound
Compound S-(+)-1E
Molecular Weight:110.1968
Molecular Formula:C8H14
InChIKey:URYYVOIYTNXXBN-OWOJBTEDSA-N
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Compound 2
Molecular Weight:796.678
Molecular Formula:C32H44O23
InChIKey:DSIKQWQNEOVDIJ-JLBZFHOGSA-N
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Compound 3
Molecular Weight:796.678
Molecular Formula:C32H44O23
InChIKey:YFBISOMQYAGYAP-JLBZFHOGSA-N
View compound in article | Full details | Search this compound
Compound 2.1Z
Molecular Weight:906.8747
Molecular Formula:C40H58O23
InChIKey:QZBXWKWROYGFOF-YOJASSQMSA-N
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