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Synthesis 2009(1): 105-112  
DOI: 10.1055/s-0028-1083266
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of 2′-Deoxyuridine and 2′-Deoxycytidine Nucleosides Bearing Bipyridine and Terpyridine Ligands at Position 5

Lubica Kalachova, Radek Pohl, Michal Hocek*
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Gilead & IOCB Research Center, Flemingovo nám. 2, 16610 Prague 6, Czech Republic
Fax: +420(2)20183559; e-Mail: hocek@uochb.cas.cz;
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Publication History

Received 3 November 2008
Publication Date:
12 December 2008 (online)

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Abstract

A methodology for the syntheses of pyrimidine (C or U) 2-deoxyribonucleosides bearing bipyridine or terpyridine ligands attached via acetylene or phenylene linkers was developed based on single step cross-coupling reactions of unprotected 5-iodopyrimidine nucleosides with bipyridine or terpyridine acetylenes of phenyl boronates. The Sonogashira reactions with acetylenes were performed in DMF, while the Suzuki reactions with boronates in water­-acetonitrile mixtures. Photophysical properties of the title modified nucleosides have been studied and (2,2′-bipyridin-5-yl)ethynyl or (2,2′-bipyridin-5-yl)phenyl derivatives exerting absorption at >300 nm and bright emission at 421-451 nm were selected as the best candidates for luminescent DNA labeling.

Key words

nucleosides - pyrimidines - bipyridines - N-ligands - cross-coupling reactions

    References

  • 1 Balzani V. Juris A. Venturi M. Chem. Rev.  1996,  96:  759 
    CrossrefPubMedGoogle Scholar
  • 2a Hurley DJ. Tor Y. J. Am. Chem. Soc.  1998,  120:  2194 
    Google Scholar
  • 2b Joshi HS. Tor Y. Chem. Commun.  2001,  549 
    Google Scholar
  • 2c Weizman H. Tor Y. J. Am. Chem. Soc.  2002,  124:  1568 
    Google Scholar
  • 2d Hurley DJ. Tor Y. J. Am. Chem. Soc.  2002,  124:  3759 
    Google Scholar
  • 2e Hurley DJ. Tor Y. J. Am. Chem. Soc.  2002,  124:  13231 
    Google Scholar
  • 2f Khan SI. Beilstein AE. Grinstaff MW. Inorg. Chem.  1999,  38:  418 
    Google Scholar
  • 2g Khan SI. Beilstein AE. Smith GD. Sykora M. Grinstaff MW. Inorg. Chem.  1999,  38:  2411 
    Google Scholar
  • 2h Telser J. Cruickshank KA. Schanze KS. Netzel TL. J. Am. Chem. Soc.  1989,  111:  7221 
    Google Scholar
  • 3 Vrábel M. Pohl R. Klepetářová B. Votruba I. Hocek M. Org. Biomol. Chem.  2007,  5:  2849 
    CrossrefGoogle Scholar
  • 4 Vrábel M. Pohl R. Votruba I. Sajadi M. Kovalenko SA. Ernsting NP. Hocek M. Org. Biomol. Chem.  2008,  6:  2852 
    CrossrefPubMedGoogle Scholar
  • 6 Vrábel M. Hocek M. Havran L. Fojta M. Votruba I. Klepetářová B. Pohl R. Rulíšek L. Zendlová L. Hobza P. Shih I. Mabery E. Mackman R. Eur. J. Inorg. Chem.  2007,  1752 
    CrossrefGoogle Scholar
  • 7 Hurley DJ. Seaman SE. Mazura JC. Tor Y. Org. Lett.  2002,  4:  2305 
    CrossrefGoogle Scholar
  • 8 Gaballah ST. Kerr CE. Eaton BE. Netzel TL. Nucleosides, Nucleotides Nucleic Acids  2002,  21:  547 
    CrossrefGoogle Scholar
  • 9 Review: Agrofoglio AL. Gillaizeau I. Saito Y. Chem. Rev.  2003,  103:  1875 
    CrossrefGoogle Scholar
  • 10 Crisp G. Flynn BL. J. Org. Chem.  1993,  58:  6614 
    CrossrefGoogle Scholar
  • 11a Garg NK. Woodroofe CC. Lacenere CJ. Quake SR. Stoltz BM. Chem. Commun.  2005,  4551 
    Google Scholar
  • 12a Amann N. Wagenknecht H.-A. Synlett  2002,  687 
    Google Scholar
  • 12b Mayer E. Valis L. Huber R. Amann N. Wagenknecht H.-A. Synthesis  2003,  2335 
    Google Scholar
  • 12c Wanninger-Weiss C. Wagenknecht H.-A. Eur. J. Org. Chem.  2008,  64 
    Google Scholar
  • For aqueous-phase cross-coupling reactions of nucleosides, see:
  • 13a Western EC. Daft JR. Johnson EM. Garnnett PM. Shoughnessy KH. J. Org. Chem.  2003,  68:  6767 
    Google Scholar
  • 13b Čapek P. Pohl R. Hocek M. Org. Biomol. Chem.  2006,  4:  2278 
    Google Scholar
  • 14 Billingsley KL. Anderson KW. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  3484 
    CrossrefPubMedGoogle Scholar
  • 15 Lakshman MK. J. Organomet. Chem.  2002,  653:  234 
    CrossrefGoogle Scholar
  • 16 Fleckenstein CA. Plenio H. Chem. Eur. J.  2008,  14:  4267 
    CrossrefGoogle Scholar
  • Our recent papers on the synthesis and polymerase incorporation of modified dNTPs:
  • 17a Čapek P. Cahová H. Pohl R. Hocek M. Gloeckner C. Marx A. Chem. Eur. J.  2007,  13:  6196 
    Google Scholar
  • 17b Brázdilová P. Vrábel M. Pohl R. Pivoňková H. Havran L. Hocek M. Fojta M. Chem. Eur. J.  2007,  13:  9527 
    Google Scholar
  • 17c Cahová H. Havran L. Brázdilová P. Pivoňková H. Pohl R. Fojta M. Hocek M. Angew. Chem. Int. Ed.  2008,  47:  2059 
    Google Scholar
  • 17d Hocek M. Fojta M. Org. Biomol. Chem.  2008,  6:  2233 
    Google Scholar
  • 18 Williams ATR. Winfield SA. Miller JN. Analyst  1983,  108:  1067 
    CrossrefGoogle Scholar
  • 19a Lakowicz JR. Principles of Fluorescence Spectroscopy   2nd ed.:  Kluwer Academic/Plenum Press; New York: 1999. 
    Google Scholar
  • 19b Handbook of Organic Photochemistry   Scaiano JC. CRC Press; Boca Raton: 1989. 
    Google Scholar
  • 19c Melhuish WH. J. Phys. Chem.  1961,  65:  229 
    Google Scholar
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Vrábel M., Horáková P., Pivoňková H., Kalachova L., Černocká H., Cahová H., Pohl R., Šebest P., Havran L., Hocek M., Fojta M.; Chem. Eur. J.; 2008, in press