Skip to main content
SpringerLink
Log in

Supramolecular photocyclodimerization of 2-hydroxyanthracene with a chiral hydrogen-bonding template, cyclodextrin and serum albumin

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

2-Hydroxyanthracene (HA) in its neutral form smoothly photocyclodimerized to four stereoisomeric [4 + 4]-cyclodimers, which were isolated and characterized for the first time, whereas the anionic form of HA turned out to be photochemically inert. Enantiodifferentiating photocyclodimerization of HA in the presence of a chiral hydrogen-bonding template (TKS159), γ-cyclodextrin (γ-CDx) and bovine serum albumin (BSA) was examined to afford chiral syn-head-to-tail and anti-head-to-head cyclodimers in modest enantiomeric excesses with TKS159 and γ-CDx, but practically no photocyclodimerization proceeded in the presence of BSA probably due to the ionization of HA in the binding sites.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Notes and references

  1. For reviews, see: A. G. Griesbeck and U. J. Meierhenrich, Asymmetric photochemistry and photochirogenesis, Angew. Chem., Int. Ed. 2002, 41, 3147.

    Article  Google Scholar 

  2. Y. Inoue and V. Ramamurthy, Chiral photochemistry, Marcel Dekker, New York, 2004.

    Book  Google Scholar 

  3. C. Müller and T. Bach, Chirality control in photochemical reactions: enantioselective formation of complex photoproducts in solution, Aust. J. Chem. 2008, 61, 557.

    Article  CAS  Google Scholar 

  4. N. Hoffmann, Photochemical reactions as key steps in organic synthesis, Chem. Rev. 2008, 108, 1052.

    Article  CAS  PubMed  Google Scholar 

  5. V. Ramamurthy and Y. Inoue, Supramolecular photochemistry, Wiley, New York, 2011.

    Book  Google Scholar 

  6. W. S. Knowles, Asymmetric hydrogenations, Angew. Chem., Int. Ed. 2002, 41, 1998.

    Article  CAS  Google Scholar 

  7. R. Noyori, Asymmetric catalysis: science and opportunities, Angew. Chem., Int. Ed. 2002, 41, 2008.

    Article  CAS  Google Scholar 

  8. K. B. Sharpless, Searching for new reactivity, Angew. Chem., Int. Ed. 2002, 41, 2024.

    Article  CAS  Google Scholar 

  9. V. Gotor, A. Alfonso and E. García-Urdiales, Asymmetric Organic Synthesis with Enzymes, Wiley-VCH, Weinheim, 2008.

    Book  Google Scholar 

  10. I. Ojima, Catalytic Asymmetric Synthesis, Wiley, Hoboken, 3rd edn, 2010.

    Book  Google Scholar 

  11. T. Bach, H. Bergmann, B. Grosch and K. Harms, Highly enantioselective intra- and intermolecular [2 + 2] photocycloaddition reactions of 2-quinolones mediated by a chiral lactam host: host–guest interactions, product configuration, and the origin of the stereoselectivity in solution, J. Am. Chem. Soc. 2002, 124, 7982.

    Article  CAS  PubMed  Google Scholar 

  12. A. Bauer, F. Westkämper, S. Grimme and T. Bach, Catalytic enantioselective reactions driven by photoinduced electron transfer, Nature 2005, 436, 1139.

    Article  CAS  PubMed  Google Scholar 

  13. D. Albrecht, F. Vogt and T. Bach, Diastereo- and enantioselective intramolecular [2 + 2] photocycloaddition reactions of 3-(ω′-alkenyl)- and 3-(ω′-alkenyloxy)-substituted 5,6-dihydro-1 H-pyridin-2-ones, Chem.–Eur. J. 2010, 16, 4284.

    Article  CAS  PubMed  Google Scholar 

  14. V. P. Rao and N. J. Turro, Asymmetric induction in benzoin by photolysis of benzaldehyde adsorbed in cyclodextrin cavities, Tetrahedron Lett. 1989, 30, 4641.

    Article  CAS  Google Scholar 

  15. For reviews, see: H.-D. Becker, Unimolecular photochemistry of anthracenes, Chem. Rev. 1993, 93, 145.

    Article  CAS  Google Scholar 

  16. H. Bouas-Laurent, A. Castellan, J.-P. Desvergne and R. Lapouyade, Photodimerization of anthracenes in fluid solution: structural aspects, Chem. Soc. Rev. 2000, 29, 43.

    Article  CAS  Google Scholar 

  17. H. Bouas-Laurent, A. Castellan, J. P. Desvergne and R. Lapouyade, Photodimerization of anthracenes in fluid solutions: (part 2) mechanistic aspects of the photocycloaddition and of the photochemical and thermal cleavage, Chem. Soc. Rev. 2001, 30, 248.

    Article  CAS  Google Scholar 

  18. A. Nakamura and Y. Inoue, Supramolecular catalysis of the enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylate by γ-cyclodextrin, J. Am. Chem. Soc. 2003, 125, 966.

    Article  CAS  PubMed  Google Scholar 

  19. A. Nakamura and Y. Inoue, Electrostatic manipulation of enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate within γ-cyclodextrin cavity through chemical modification. Inverted product distribution and enhanced enantioselectivity, J. Am. Chem. Soc. 2005, 127, 5338.

    Article  CAS  PubMed  Google Scholar 

  20. C. Yang, G. Fukuhara, A. Nakamura, Y. Origane, K. Fujita, D.-Q. Yuan, T. Mori, T. Wada and Y. Inoue, Enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylate catalyzed by 6A,6X-diamino-6A,6X-dideoxy-γ-cyclodextrins: manipulation of product chirality by electrostatic interaction, temperature and solvent in supramolecular photochirogenesis, J. Photochem. Photobiol., A: Chem. 2005, 173, 375.

    Article  CAS  Google Scholar 

  21. C. Yang, A. Nakamura, G. Fukuhara, Y. Origane, T. Mori, T. Wada and Y. Inoue, Pressure and temperature-controlled enantiodifferentiating [4 + 4] photocyclodimerization of 2-anthracenecarboxylate mediated by secondary face- and skeleton-modified γ-cyclodextrins, J. Org. Chem. 2006, 71, 3126.

    Article  CAS  PubMed  Google Scholar 

  22. C. Yang, A. Nakamura, T. Wada and Y. Inoue, Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid mediated by γ-cyclodextrins with a flexible or rigid cap, Org. Lett. 2006, 8, 3005.

    Article  CAS  PubMed  Google Scholar 

  23. C. Yang, M. Nishijima, A. Nakamura, T. Mori, T. Wada and Y. Inoue, A remarkable stereoselectivity switching upon solid-state versus solution-phase enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid mediated by native and 3,6-anhydro-γ-cyclodextrins, Tetrahedron Lett. 2007, 48, 4357.

    Article  CAS  Google Scholar 

  24. C. Yang, T. Mori and Y. Inoue, Supramolecular enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate mediated by capped γ-cyclodextrins: critical control of enantioselectivity by cap rigidity, J. Org. Chem. 2008, 73, 5786.

    Article  CAS  PubMed  Google Scholar 

  25. H. Qiu, C. Yang, Y. Inoue and S. Che, Supramolecular photochirogenesis with cyclodextrin-silica composite. Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate with mesoporous silica wall-capped γ-cyclodextrin, Org. Lett. 2009, 11, 1793.

    Article  CAS  PubMed  Google Scholar 

  26. C. Ke, C. Yang, T. Mori, T. Wada, Y. Liu and Y. Inoue, Catalytic enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid mediated by a non-sensitizing chiral metallosupramolecular host, Angew. Chem., Int. Ed. 2009, 48, 6675.

    Article  CAS  Google Scholar 

  27. C. Ke, C. Yang, W. Liang, T. Mori, Y. Liu and Y. Inoue, Critical stereocontrol by inter-amino distance of supramolecular photocyclodimerization of 2-anthracenecarboxylate mediated by 6-(ω-aminoalkylamino)-γ-cyclodextrins, New J. Chem. 2010, 34, 1323.

    Article  CAS  Google Scholar 

  28. Q. Wang, C. Yang, G. Fukuhara, T. Mori, Y. Liu and Y. Inoue, Supramolecular FRET photocyclodimerization of anthracenecarboxylate with naphthalene-capped γ-cyclodextrin, Beilstein J. Org. Chem. 2011, 7, 290.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Q. Wang, C. Yang, C. Ke, G. Fukuhara, T. Mori, Y. Liu and Y. Inoue, Wavelength-controlled supramolecular photocyclodimerization of anthracenecarboxylate mediated by γ-cyclodextrins, Chem. Commun. 2011, 47, 6849.

    Article  CAS  Google Scholar 

  30. J. Mizoguchi, Y. Kawanami, T. Wada, K. Kodama, K. Anzai, T. Yanagi and Y. Inoue, Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid using a chiral N-(2-hydroxymethyl-4-pyrrolidinyl)benzamide template, Org. Lett. 2006, 8, 6051.

    Article  CAS  PubMed  Google Scholar 

  31. Y. Kawanami, T. C. S. Pace, J. Mizoguchi, T. Yanagi, M. Nishijima, T. Mori, T. Wada, C. Bohne and Y. Inoue, Supramolecular complexation and enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid with 4-aminoprolinol derivatives as chiral hydrogen-bonding templates, J. Org. Chem. 2009, 74, 7908.

    Article  CAS  PubMed  Google Scholar 

  32. Y. Kawanami, S. Katsumata, J. Mizoguchi, M. Nishijima, G. Fukuhara, C. Yang, T. Mori and Y. Inoue, Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid via competitive binary/ternary hydrogen-bonded complexes with 4-benzamidoprolinol, Org. Lett. 2012, 14, 4962.

    Article  CAS  PubMed  Google Scholar 

  33. Y. Kawanami, H. Umehara, J. Mizoguchi, M. Nishijima, G. Fukuhara, C. Yang, T. Mori and Y. Inoue, Cross- versus homo-photocyclodimerization of anthracene and 2-anthracenecarboxylic acid mediated by a chiral hydrogen-bonding template. Factors controlling the cross-/homo-selectivity and enantioselectivity, J. Org. Chem. 2013, 78, 3073.

    Article  CAS  PubMed  Google Scholar 

  34. T. Wada, M. Nishijima, T. Fujisawa, N. Sugahara, T. Mori, A. Nakamura and Y. Inoue, Bovine serum albumin-mediated enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate, J. Am. Chem. Soc. 2003, 125, 7492.

    Article  CAS  PubMed  Google Scholar 

  35. M. Nishijima, T. C. S. Pace, A. Nakamura, T. Mori, T. Wada, C. Bohne and Y. Inoue, Supramolecular photochirogenesis with biomolecules. Mechanistic studies on the enantiodifferentiation for the photocyclodimerization of 2-anthracenecarboxylate mediated by bovine serum albumin, J. Org. Chem. 2007, 72, 2707.

    Article  CAS  PubMed  Google Scholar 

  36. M. Nishijima, T. Wada, T. Mori, T. C. S. Pace, C. Bohne and Y. Inoue, Highly enantiomeric supramolecular [4 + 4] photocyclodimerization of 2-anthracenecarboxylate mediated by human serum albumin, J. Am. Chem. Soc. 2007, 129, 3478.

    Article  CAS  PubMed  Google Scholar 

  37. T. C. S. Pace, M. Nishijima, T. Wada, Y. Inoue and C. Bohne, Photophysical studies on the supramolecular photochirogenesis for the photocyclodimerization of 2-anthracenecarboxylate within human serum albumin, J. Phys. Chem. B 2009, 113, 10445.

    Article  CAS  PubMed  Google Scholar 

  38. K. Bando, T. Zako, M. Sakono, M. Maeda, T. Wada, M. Nishijima, G. Fukuhara, C. Yang, T. Mori, T. C. S. Pace, C. Bohne and Y. Inoue, Bio-supramolecular photochirogenesis with molecular chaperone: enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate mediated by prefoldin, Photochem. Photobiol. Sci. 2010, 9, 655.

    Article  CAS  PubMed  Google Scholar 

  39. D. Fuentealba, H. Kato, M. Nishijima, G. Fukuhara, T. Mori, Y. Inoue and C. Bohne, Explaining the highly enantiomeric photocyclodimerization of 2-anthracenecarboxylate bound to human serum albumin using time-resolved anisotropy studies, J. Am. Chem. Soc. 2013, 135, 203.

    Article  CAS  PubMed  Google Scholar 

  40. A. Bujacz, Structure of bovine, equine and leporine serum albumin, Acta Crystallogr., Sect. D: Biol. Crystallogr. 2012, D68, 1278. (b) Protein Data Bank Japan (PDBj), ID: 4f5s

    Article  CAS  Google Scholar 

  41. R. S. Coleman and M. A. Mortensen, Stereocontrolled synthesis of anthracene β- C-ribosides: fluorescent probes for photophysical studies of DNA, Tetrahedron Lett. 2003, 44, 1215.

    Article  CAS  Google Scholar 

  42. T. Yanagi, A. Kitajima, K. Anzai, K. Kodama, J. Mizoguchi, H. Fujiwara, H. Sakiyama, O. Kamoda and C. Kamei, Synthesis and pharmacological activity of 4-amino-5-chloro-2-methoxy- N-[(2 S,4 S)-1-ethyl-2-hydroxymethyl-4-pyrrolidinyl]benzamide (TKS159) and its optical isomers, Chem. Pharm. Bull. 1999, 47, 1650.

    Article  CAS  Google Scholar 

  43. L. M. Rubeko and B. M. Uzhinov, Photoprotolytic reactions of 2-anthrol, J. Appl. Spectrosc. 1979, 30, 470.

    Article  CAS  Google Scholar 

  44. E. V. Donckt and G. Porter, Acidity constants of anthracene derivatives in singlet and triplet excited states, Trans. Faraday Soc. 1968, 64, 3218.

    Article  Google Scholar 

  45. E. L. Wehry and L. B. Rogers, Application of linear free energy relations to electronically excited states of monosubstituted phenols, J. Am. Chem. Soc. 1965, 87, 4234.

    Article  CAS  Google Scholar 

  46. H. Baba and S. Suzuki, Electronic spectra and hydrogen bonding. I. Phenol and naphthols, J. Chem. Phys. 1961, 35, 1118.

    Article  CAS  Google Scholar 

  47. F. D. Greene, Problems of stereochemistry in photochemical reactions in the anthracene area, Bull. Soc. Chim. Fr. 1960 1356.

    Google Scholar 

  48. N. Levi-Minzi and M. Zandomeneghi, Photochemistry in biological matrices: activation of racemic mixtures and interconversion of enantiomers, J. Am. Chem. Soc. 1992, 114, 9300.

    Article  CAS  Google Scholar 

  49. A. Ouchi, G. Zandomeneghi and M. Zandomeneghi, Complexation with albumins of chiral aromatic substrates and their chemistry in ground and excited states. Catalytic and chirality recognition properties of the protein in the cases of binaphthol, its photoisomers, and ketoprofen, Chirality 2002, 14, 1.

    Article  CAS  PubMed  Google Scholar 

  50. M. Nishijima, J.-W. Chang, C. Yang, G. Fukuhara, T. Mori and Y. Inoue, Chiral recognition and supramolecular photoreaction of 1,1′-binaphthol with bovine and human serum albumins, Res. Chem. Intermed. 2013, 39, 371.

    Article  CAS  Google Scholar 

  51. M. Kajtar, C. Horvath-Toro, E. Kuthi and J. Szejtli, A simple rule for predicting circular dichroism induced in aromatic guests by cyclodextrin hosts in inclusion complexes, Acta Chim. Acad. Sci. Hung. 1982, 110, 327.

    CAS  Google Scholar 

  52. N. Harada and K. Nakanishi, Circular dichronic spectroscopy–exciton coupling in organic stereochemistry, University Science Books, Mill Valley, CA, 1983.

    Google Scholar 

  53. N. Berova, L. D. Bari and G. Pescitelli, Application of electronic circular dichroism in configuration and conformational analysis of organic compounds, Chem. Soc. Rev. 2007, 36, 914.

    Article  CAS  PubMed  Google Scholar 

  54. A. K. Mishra, M. Sato, H. Hiratsuka and H. Shizuka, Dual emission from ion pairs produced by excited-state proton transfer in the naphthol-amine system at 77 K, J. Chem. Soc., Faraday Trans. 1991, 87, 1311.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

    Gaku Fukuhara, Hiroaki Umehara, Saki Higashino, Tadashi Mori & Yoshihisa Inoue

  2. Office for University–Industry Collaboration, Osaka University, 2-1 Yamada-oka, Suita, 565-0871, Japan

    Masaki Nishijima & Cheng Yang

  3. College of Chemistry, Sichuan University, Chengdu, 610064, China

    Cheng Yang

  4. Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai, 980-8577, Japan

    Takehiko Wada

Authors
  1. Gaku Fukuhara
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hiroaki Umehara
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Saki Higashino
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Masaki Nishijima
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Cheng Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tadashi Mori
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Takehiko Wada
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Yoshihisa Inoue
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yoshihisa Inoue.

Additional information

This article is dedicated to the warm memory of Prof. Nicholas John Turro.

Electronic supplementary information (ESI) available: UV-vis spectral change of HA upon photoirradiation and HPLC, NMR and mass charts of the cyclodimers 1–4. See DOI: 10.1039/c3pp50127b

Rights and permissions

Reprints and permissions

About this article

Cite this article

Fukuhara, G., Umehara, H., Higashino, S. et al. Supramolecular photocyclodimerization of 2-hydroxyanthracene with a chiral hydrogen-bonding template, cyclodextrin and serum albumin. Photochem Photobiol Sci 13, 162–171 (2014). https://doi.org/10.1039/c3pp50127b

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c3pp50127b

Search

Navigation