Monatshefte für Chemie - Chemical Monthly

, Volume 141, Issue 3, pp 339–349 | Cite as

Synthesis of novel symmetrical, single-chain, diacetylene-modified bolaamphiphiles with different alkyl chain lengths

  • Simon Drescher
  • Katrin Helmis
  • Andreas Langner
  • Bodo Dobner
Original Paper


General syntheses of novel symmetrical, single-chain, diacetylene-modified bolaphospholipids have been carried out in five steps. For the ω-alkynols, which have an important role as key intermediates, three different synthetic approaches were comprehensively investigated. For the final synthesis it is suggested that (1) alkylation of lithium (trimethylsilyl)acetylide with tetrahydropyranyl-protected ω-bromoalcohols, followed by (2) cleavage of the trimethylsilyl moiety and the tetrahydropyranyl protecting group, and (3) copper(II)-catalyzed Eglinton coupling is the best strategy for obtaining diacetylene-modified alkane-1,ω-diols, because higher yields were obtained while avoiding the formation of by-products. Moreover, conversion of the diols into bipolar phospholipids was achieved by bis-phosphorylation with β-bromoethylphosphoric acid dichloride and subsequent quaternization with trimethylamine or dimethylamine. Finally, spectral data are presented for novel single-chain, diacetylene-modified bolaphospholipids with promising potential as starting molecules in the formation of polymerizable and, thus, thermostable nanofibers.

Graphical abstract


Alkynes Diacetylenes Lipids Nanostructures Phosphates Phospholipids 



We are grateful to the Deutsche Forschungsgemeinschaft (DFG) for financial support.


  1. 1.
    Fuhrhop JH, Wang T (2004) Chem Rev 104:2901CrossRefGoogle Scholar
  2. 2.
    Meister A, Blume A (2007) Curr Opin Colloid Interface Sci 12:138CrossRefGoogle Scholar
  3. 3.
    Sprott GD, Tolson DL, Patel GB (1997) FEMS Microbiol Lett 154:17CrossRefGoogle Scholar
  4. 4.
    Cornell BA, Braach-Maksvytis VBL, King GL, Osman PDJ, Raguse B, Wieczorek L (1997) Nature 387:580CrossRefGoogle Scholar
  5. 5.
    Benvegnu T, Brard M, Plusquellec D (2004) Curr Opin Colloid Interface Sci 8:469CrossRefGoogle Scholar
  6. 6.
    Newkome GR, Baker GR, Arai S, Saunders MJ, Russo PS, Theriot KJ, Moorefield CN, Rogers LE, Miller JE, Lieux TR, Murray ME, Phillips B, Pascal L (1990) J Am Chem Soc 112:8458CrossRefGoogle Scholar
  7. 7.
    Iwaura R, Yoshida K, Masuda M, Yase K, Shimizu T (2002) Chem Mater 14:3047CrossRefGoogle Scholar
  8. 8.
    Drescher S, Meister A, Blume A, Karlsson G, Almgren M, Dobner B (2007) Chem Eur J 13:5300CrossRefGoogle Scholar
  9. 9.
    Köhler K, Förster G, Hauser A, Dobner B, Heiser UF, Ziethe F, Richter W, Steiniger F, Drechsler M, Stettin H, Blume A (2004) Angew Chem Int Ed 43:245CrossRefGoogle Scholar
  10. 10.
    Köhler K, Forster G, Hauser A, Dobner B, Heiser UF, Ziethe F, Richter W, Steiniger F, Drechsler M, Stettin H, Blume A (2004) J Am Chem Soc 126:16804CrossRefGoogle Scholar
  11. 11.
    Meister A, Drescher S, Mey I, Wahab M, Graf G, Garamus VM, Hause G, Mogel HJ, Janshoff A, Dobner B, Blume A (2008) J Phys Chem B 112:4506CrossRefGoogle Scholar
  12. 12.
    Köhler K, Meister A, Förster G, Dobner B, Drescher S, Ziethe F, Richter W, Steiniger F, Drechsler M, Hause G, Blume A (2006) Soft Matter 2:77CrossRefGoogle Scholar
  13. 13.
    Meister A, Drescher S, Garamus VM, Karlsson G, Graf G, Dobner B, Blume A (2008) Langmuir 24:6238CrossRefGoogle Scholar
  14. 14.
    Inoue K, One Y, Kanekiyo Y, Hanabusa K, Shinkai S (1999) Chem Lett 28:429CrossRefGoogle Scholar
  15. 15.
    George M, Weiss RG (2003) Chem Mater 15:2879CrossRefGoogle Scholar
  16. 16.
    Shirakawa M, Fujita N, Shinkai S (2005) J Am Chem Soc 127:4164CrossRefGoogle Scholar
  17. 17.
    Charych D, Cheng Q, Reichert A, Kuziemko G, Stroh M, Nagy JO, Spevak W, Stevens RC (1996) Chem Biol 3:113CrossRefGoogle Scholar
  18. 18.
    Song J, Cheng Q, Zhu S, Stevens RC (2002) Biomed Microdevices 4:213CrossRefGoogle Scholar
  19. 19.
    Song J, Cisar JS, Bertozzi CR (2004) J Am Chem Soc 126:8459CrossRefGoogle Scholar
  20. 20.
    Reppy MA, Pindzola BA (2007) Chem Commun 4317Google Scholar
  21. 21.
    Ahn DJ, Kim JM (2008) Acc Chem Res 41:805CrossRefGoogle Scholar
  22. 22.
    Drescher S, Meister A, Graf G, Hause G, Blume A, Dobner B (2008) Chem Eur J 14:6796CrossRefGoogle Scholar
  23. 23.
    Corey EJ, Katzenellenbogen JA, Gilman NW, Roman SA, Erickson BW (1968) J Am Chem Soc 90:5618CrossRefGoogle Scholar
  24. 24.
    Corey EJ, Katzenellenbogen JA, Roman SA, Gilman NW (1971) Tetrahedron Lett 12:1821CrossRefGoogle Scholar
  25. 25.
    Takano S, Sugihara T, Ogasawara K (1991) Synlett 279Google Scholar
  26. 26.
    Brown CA, Yamashita A (1975) J Am Chem Soc 97:891CrossRefGoogle Scholar
  27. 27.
    Macaulay SR (1980) J Org Chem 45:734CrossRefGoogle Scholar
  28. 28.
    Oppolzer W, Radinov RN, El-Sayed E (2001) J Org Chem 66:4766CrossRefGoogle Scholar
  29. 29.
    Schwarz M, Waters RM (1972) Synthesis 567Google Scholar
  30. 30.
    Godt A, Duda S, Ünsal Ö, Thiel J, Härter A, Roos M, Tschierske C, Diele S (2002) Chem Eur J 8:5094CrossRefGoogle Scholar
  31. 31.
    Carballeira NM, Montano N, Padilla LF (2007) Chem Phys Lipids 145:37CrossRefGoogle Scholar
  32. 32.
    Menger FM, Chen XY, Brocchini S, Hopkins HP, Hamilton D (1993) J Am Chem Soc 115:6600CrossRefGoogle Scholar
  33. 33.
    Eglinton G, Galbraith AR (1959) J Chem Soc 889Google Scholar
  34. 34.
    Hirt G, Berechthold R (1958) Pharm Acta Helv 33:349Google Scholar
  35. 35.
    van Aar MPM, Thijs L, Zwanenburg B (1995) Tetrahedron 51:11223CrossRefGoogle Scholar
  36. 36.
    Kinsho T, Mori K (1989) Agric Biol Chem 53:2785Google Scholar
  37. 37.
    Grimmer G, Hildebrandt A (1965) Justus Liebigs Ann Chem 685:154CrossRefGoogle Scholar
  38. 38.
    Sammul OR, Hollingsworth CA, Wotiz JH (1953) J Am Chem Soc 75:4856CrossRefGoogle Scholar
  39. 39.
    Christie WW, Holman RT (1967) Chem Phys Lipids 1:407CrossRefGoogle Scholar
  40. 40.
    Augustin KE, Schäfer HJ (1991) Liebigs Ann Chem 1037Google Scholar

Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Simon Drescher
    • 1
  • Katrin Helmis
    • 1
  • Andreas Langner
    • 1
  • Bodo Dobner
    • 1
  1. 1.Department of Biochemical Pharmacy, Institute of PharmacyMartin-Luther-University Halle-WittenbergHalle (Saale)Germany

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