Skip to main content
SpringerLink
Log in

Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems

  • Published:
Research on Chemical Intermediates Aims and scope Submit manuscript

Abstract

To synthesize sulfur-containing π-conjugated polymers, reaction conditions for rhodium-catalyzed hydrothiolation of terminal alkynes with arenethiols are optimized in detail. Under the optimized conditions, rhodium-catalyzed hydrothiolation of terminal alkynes proceeds regio- and stereoselectively to afford the corresponding vinyl sulfides via an anti-Markovnikov and syn-addition process. Then, the rhodium-catalyzed hydrothiolation is applied to polymerization of 2,5-diethynylthiophene with benzene-1,4-dithiol, which successfully provides sulfur-containing π-conjugated polymers with excellent regio- and stereoselectivities.

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
Scheme 3
Scheme 4
Scheme 5
Scheme 6
Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. P. Kovacic, M.B. Jones, Chem. Rev. 87, 357 (1987)

    Article  CAS  Google Scholar 

  2. T. Yamamoto, I. Yamaguchi, T. Yasuda, in Advances in Polymer Science, ed. by C. Weder (Springer, Heidelberg, 2005), p. 181

    Google Scholar 

  3. J.E. Anthony, Chem. Rev. 106, 5028 (2006)

    Article  CAS  Google Scholar 

  4. A.R. Murphy, J.M.J. Fréchet, Chem. Rev. 107, 1066 (2007)

    Article  CAS  Google Scholar 

  5. S. Gunes, H. Neugebauer, N.S. Sariciftci, Chem. Rev. 107, 1324 (2007)

    Article  Google Scholar 

  6. S.W. Thomas, G.D. Joly, T.M. Swager, Chem. Rev. 107, 1339 (2007)

    Article  CAS  Google Scholar 

  7. J. Liu, J.W.Y. Lam, B.Z. Tang, Chem. Rev. 109, 5799 (2009)

    Article  CAS  Google Scholar 

  8. C.-K. Tai, Y.-J. Chen, H.-W. Chang, P.-L. Yeh, B.-C. Wang, Comput. Theor. Chem. 971, 42 (2011)

    Article  CAS  Google Scholar 

  9. C.-H. Hsieh, Ö.F. Erdem, S.D. Harman, M.L. Singleton, E. Reijerse, W. Lubitz, C.V. Popescu, J.H. Reibenspies, S.M. Brothers, M.B. Hall, M.Y. Darensbourg, J. Am. Chem. Soc. 134, 13089 (2012)

    Article  CAS  Google Scholar 

  10. T. Yamamoto, J. Organomet. Chem. 653, 195 (2002)

    Article  CAS  Google Scholar 

  11. T. Yamamoto, Synlett. 14, 425 (2003)

  12. H. Katayama, M. Nagao, T. Nishimura, Y. Matsui, K. Umeda, K. Akamatsu, T. Tsuruoka, H. Nawafune, F. Ozawa, J. Am. Chem. Soc. 127, 4350 (2005)

    Article  CAS  Google Scholar 

  13. R. Miyakoshi, A. Yokoyama, T. Yokozawa, J. Am. Chem. Soc. 127, 49 (2005)

    Article  Google Scholar 

  14. T. Yamamoto, T.-A. Koizumi, Polymer 48, 5449 (2007)

    Article  CAS  Google Scholar 

  15. K. Nakagawa, I. Tomita, Macromolecules 40, 9212 (2007)

    Article  CAS  Google Scholar 

  16. J. Sakamoto, M. Rehahn, G. Wegner, A.D. Schlüter, Macromol. Rapid Commun. 30, 653 (2009)

    Article  CAS  Google Scholar 

  17. B. Hohl, L. Bertschi, X. Zhang, A.D. Schlüter, J. Sakamoto, Macromolecules 45, 5418 (2012)

    Article  CAS  Google Scholar 

  18. Y.Y. Durmaz, E.L. Sahkulubey, Y. Yagci, E. Martinelli, G. Galli, J. Polym. Sci. A Polym. Chem. 50, 4911 (2012)

    Article  CAS  Google Scholar 

  19. H–.H. Chen, H.-A. Lin, S.-C. Chien, T.-H. Wang, H.-F. Hsu, T.-L. Shih, C. Wu, J. Mater. Chem. 22, 12718 (2012)

    Article  CAS  Google Scholar 

  20. L.L. Hegedus, R.W. McCabe, Catalyst Poisoning (Marcel Dekker, New York, 1984)

    Google Scholar 

  21. A. Ogawa, N. Sonoda, J. Synth. Org. Chem. Jpn. 54, 894 (1996)

    Article  CAS  Google Scholar 

  22. L.-B. Han, M. Tanaka, Chem. Commun. 5, 395 (1999)

  23. A. Ogawa, J. Organomet. Chem. 611, 463 (2000)

    Article  CAS  Google Scholar 

  24. T. Kondo, T. Mitsudo, Chem. Rev. 100, 3205 (2000)

    Article  CAS  Google Scholar 

  25. F. Alonso, I.P. Beletskaya, M. Yus, Chem. Rev. 104, 3079 (2004)

    Article  CAS  Google Scholar 

  26. I. Beletskaya, C. Mobarg, Chem. Rev. 106, 2320 (2006)

    Article  CAS  Google Scholar 

  27. H. Kuniyasu, N. Kambe, Chem. Lett. 35, 1320 (2006)

    Article  CAS  Google Scholar 

  28. P. Bichler, J.A. Love, in Topics in Organometallic Chemistry, ed. by A. Vigalok (Springer, Heidelberg, 2010), p. 31

    Google Scholar 

  29. I.P. Beletskaya, V.P. Ananikov, Chem. Rev. 111, 1596 (2011)

    Article  CAS  Google Scholar 

  30. A. Ogawa, in Topics in Organometallic Chemistry, ed. by V.P. Ananikov, M. Tanaka (Springer, Heidelberg, 2013), p. 43

    Google Scholar 

  31. H. Kuniyasu, A. Ogawa, K. Sato, I. Ryu, N. Kambe, N. Sonoda, J. Am. Chem. Soc. 114, 5902 (1992)

    Article  CAS  Google Scholar 

  32. A. Ogawa, T. Ikeda, K. Kimmura, T. Hirao, J. Am. Chem. Soc. 121, 5108 (1999)

    Article  CAS  Google Scholar 

  33. T. Ikeda, N. Nakagawa, A. Nomoto, Y. Minatobe, S. Fuluzawa, T. Hirao, A. Ogawa, J. Mater. Sci. Eng. B 3, 423 (2013)

    CAS  Google Scholar 

  34. D.L. Pearson, J.M. Tour, J. Org. Chem. 62, 1376 (1997)

    Article  CAS  Google Scholar 

  35. T. Okamoto, T. Kakinami, H. Fujimoto, S. Kajigaeshi, Bull. Chem. Soc. Jpn. 6, 2566 (1991)

    Article  Google Scholar 

  36. T.X. Neenan, G.M. Whitesides, J. Org. Chem. 53, 2489 (1998)

    Article  Google Scholar 

Download references

Acknowledgments

We thank Dr. Takuma Ikeda and Mr. Kouichi Kimura for their experimental support.

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka, 599-8531, Japan

    Aya Yoshimura, Akihiro Nomoto & Akiya Ogawa

Authors
  1. Aya Yoshimura
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Akihiro Nomoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Akiya Ogawa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Akiya Ogawa.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yoshimura, A., Nomoto, A. & Ogawa, A. Rhodium-catalyzed hydrothiolation of alkynes with thiols for construction of sulfur-containing π-conjugated systems. Res Chem Intermed 40, 2381–2389 (2014). https://doi.org/10.1007/s11164-014-1639-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11164-014-1639-0

Search

Navigation