Skip to main content
SpringerLink
Log in

Synthesis of an Aza Chiral Crown Ether Grafted to Nanofibrous Silica Support and Application in Asymmetric Michael Addition

  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Abstract

We report on the synthesis of a new, supported phase transfer catalyst and its asymmetric induction. An inorganic-polymer-supported chiral crown ether was prepared by the reaction between an optically active macrocycle deriving from methyl-α-d-glucopyranoside and silica nanofibres. The inorganic carrier of the catalyst has high specific surface area due to its nanofibrous structure, which is favourable for heterogeneous catalytic reactions. SiO2 fibres were electrospun from silica sol which was prepared via sol–gel reactions from tetraethylorthosilicate. The asymmetric Michael reaction of diethyl acetamidomalonate and β-nitrostyrene was selected for the comparison of the performance of various glucopyranoside-based macrocycles. The asymmetric inductions of macrocycles provided 20–99 % enantiomeric excess. A triethoxysilyl derivative was prepared from the highly enantioselective macrocycle in order to immobilize it on the surface of the silica nanofibres. The supported glucose based monoaza-15-crown-5 type macrocycle was characterized by X-ray photoelectron spectroscopy and compared with non-supported native crown ethers in the asymmetric Michael addition. The immobilized phase-transfer catalyst generated high enantiomeric excess (82 %) in spite of the fact that it was used in a three-phase reaction.

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

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Scheme 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. M. Breuer, K. Ditrich, T. Habicher, B. Hauer, M. Kesseler, R. Stürmer, T. Zelinski, Angew. Chem. Int. Ed. 43, 788 (2004)

    Article  CAS  Google Scholar 

  2. T. Ooi, K. Maruoka, Angew. Chem. Int. Ed. 46, 4222 (2007)

    Article  CAS  Google Scholar 

  3. K. Maruoka (ed.), Asymmetric Phase Transfer Catalysis (WILEY-VCH, Weinheim, 2008)

    Google Scholar 

  4. R. Chinchilla, P. Mazo, C. Nájera, Tetrahedron-Asymmetry 11, 3277 (2000)

    Article  CAS  Google Scholar 

  5. O. Sadeghi, M.M. Amini, M.F.B. Bazargani, A. Mehrani, A. Aghabali, M. Adineh, V. Amani, K. Mehrani, J Inorg Organomet Polym Mater 22, 530 (2011)

    Article  Google Scholar 

  6. P.L. Anelli, B. Czech, F. Montanari, S. Quici, J. Am. Chem. Soc. 106, 861 (1984)

    Article  CAS  Google Scholar 

  7. S. Colonna, R. Fornasier, U. Pfeiffer, J. Chem. Soc. Perkin. Trans. 1(2), 8 (1978)

    Article  Google Scholar 

  8. Z. Zhengpu, W. Yongmer, W. Zhen, P. Hodge, React. Funct. Polym. 41, 37 (1999)

    Article  Google Scholar 

  9. A. Corma, S. Iborra, M. Iglesias, F. Sánchez, Catal. Lett. 82, 237 (2002)

    Article  CAS  Google Scholar 

  10. H. Watanabe, T. Iijima, W. Fukuda, M. Tomoi, React. Funct. Polym. 37, 101 (1998)

    Article  CAS  Google Scholar 

  11. T. Bakó, P. Bakó, G. Keglevich, P. Bombicz, M. Kubinyi, K. Pál, S. Bodor, A. Makó, L. Tőke, Tetrahedron-Asymmetry 15, 1589 (2004)

    Article  Google Scholar 

  12. S. Aoki, S. Sasaki, K. Koga, Tetrahedron Lett. 30, 7229 (1989)

    Article  CAS  Google Scholar 

  13. P. Bakó, E. Czinege, T. Bakó, L. Tőke, Tetrahedron-Asymmetry 10, 4539 (1999)

    Article  Google Scholar 

  14. T. Akiyama, M. Hara, K. Fuchibe, S. Sakamoto, K. Yamaguchi, Chem. Commun. 1734 (2003)

  15. P. Bakó, Z. Rapi, G. Keglevich, T. Szabó, P.L. Sóti, T. Vígh, A. Grűn, T. Holczbauer, Tetrahedron Lett. 52, 1473 (2011)

    Article  Google Scholar 

  16. D.J. Cram, G.D.Y. Sogah, Chem. Commun. 18 (1981)

  17. S.D. Alexandratos, C.L. Stine, React. Funct. Polym. 60, 3 (2004)

    Article  CAS  Google Scholar 

  18. P. Bakó, K. Vízvárdi, S. Toppet, E. Van der Eycken, G.J. Hoornaert, L. Tőke, Tetrahedron 54, 14975 (1998)

    Article  Google Scholar 

  19. P. Bakó, L. Tőke, J. Inclus, Phenom. Mol. 23, 195 (1995)

    Google Scholar 

  20. S. Murugesan, G.S. Sur, J.E. Mark, G. Beaucage, J Inorg Organomet Polym Mater 14, 239 (2004)

    Article  CAS  Google Scholar 

  21. Z. Ma, H. Ji, Y. Teng, G. Dong, J. Zhou, D. Tan, J. Qiu, J. Colloid, Interface Sci. 358, 547 (2011)

    Article  CAS  Google Scholar 

  22. S. Choi, S. Lee, S. Im, S. Kim, Y. Joo, J. Mater. Sci. Lett. 22, 891 (2003)

    Article  CAS  Google Scholar 

  23. S. Ek, A. Root, M. Peussa, L. Niinistö, Thermochim. Acta 379, 201 (2001)

    Article  CAS  Google Scholar 

  24. J. Kupai, S. Lévai, K. Antal, G.T. Balogh, T. Tóth, P. Huszthy, Tetrahedron-Asymmetry 23, 415 (2012)

    Article  CAS  Google Scholar 

  25. T. Tunç, İ. Uslu, Ş. Durmuşoğlu, S. Keskin, A. Aytimur, A. Akdemir, J Inorg Organomet Polym Mater 22, 105 (2011)

    Article  Google Scholar 

  26. J. Kelly, D.C. Sherrington, Polymer 25, 1499 (1984)

    Article  CAS  Google Scholar 

  27. H.S. Kim, Y.-M. Song, J.S. Choi, J.W. Yang, H. Han, Tetrahedron 60, 12051 (2004)

    Article  CAS  Google Scholar 

  28. W.H. Lee, S.J. Kim, W.J. Lee, J.G. Lee, R.C. Haddon, P.J. Reucroft, Appl. Surf. Sci. 181, 121 (2001)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The research was supported by the OTKA Research Fund (code 82426). Besides this project is supported by the New Széchenyi Plan (Project ID: TÁMOP-4.2.1/B-09/1/KMR-2010-0002).

Author information

Authors and Affiliations

  1. Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Budafoki út 8, Budapest, 1111, Hungary

    Péter L. Sóti, Lőrinc Telkes, Zsolt Rapi, Tamás Vigh, Zsombor K. Nagy, Péter Bakó & György Marosi

  2. Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri út 59-67, Budapest, 1025, Hungary

    András Tóth

Authors
  1. Péter L. Sóti
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lőrinc Telkes
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zsolt Rapi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. András Tóth
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tamás Vigh
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zsombor K. Nagy
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Péter Bakó
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. György Marosi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to György Marosi.

Additional information

Péter Bakó and György Marosi have contributed equally to this work.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sóti, P.L., Telkes, L., Rapi, Z. et al. Synthesis of an Aza Chiral Crown Ether Grafted to Nanofibrous Silica Support and Application in Asymmetric Michael Addition. J Inorg Organomet Polym 24, 713–721 (2014). https://doi.org/10.1007/s10904-014-0037-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10904-014-0037-9

Keywords

Search

Navigation