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 


  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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