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Synthesis 2001(14): 2156-2164
DOI: 10.1055/s-2001-18067
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis and Photoreaction of 4"-Pivaloyl Guanosides

Martin Spormann, Bernd Giese*
Department of Chemistry, University of Basel, St. Johanns Ring 19, 4056 Basel, Switzerland
Fax: +41(61)2671105; e-Mail: bernd.giese@unibas.ch;
Further Information

Publication History

Received 29 June 2001
Publication Date:
09 August 2004 (online)

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Abstract

The synthesis of a 4’-pivaloylated guanosine and its incorporation into oligonucleotides is described. Photolysis of the modified nucleoside and DNA double strand leads in nearly quantitative yield to enol ethers. The decisive step in this reaction is a very fast electron transfer from guanine to an enol ether radical cation.

Key words

nucleosides - oligonucleotides - radicals - electron transfer - photochemistry

    References

  • 1 Eley DD. Spivey DI. Trans. Faraday Soc.  1962,  58:  411 
    CrossrefGoogle Scholar
  • 2a Schuster GB. Acc. Chem. Res.  2000,  33:  253 
    CrossrefGoogle Scholar
  • 2b Giese B. Acc. Chem. Res.  2000,  33:  631 
    CrossrefGoogle Scholar
  • 2c Wan C. Fiebig T. Schiemann O. Barton JK. Zewail AH. Proc. Natl. Acad. Sci. U. S. A.  2000,  97:  14052 
    CrossrefGoogle Scholar
  • 2d Lewis FD. Letsinger RL. Wasielewski MR. Acc. Chem. Res.  2001,  34:  159 
    CrossrefGoogle Scholar
  • 3a Meggers E. Michel-Beyerle ME. Giese B. J. Am. Chem. Soc.  1998,  120:  12950 
    Google Scholar
  • 3b Giese B. Wessely S. Spormann M. Lindemann U. Meggers E. Michel-Beyerle ME. Angew. Chem., Int. Ed.  1999,  38:  996 
    Google Scholar
  • 4a Giese B. Spichty M. ChemPhysChem.  2000,  1:  195 
    CrossrefGoogle Scholar
  • 4b Giese B. Amaudrut J. Köhler A.-K. Spormann M. Wessely S. Nature  2001,  412:  318 
    CrossrefGoogle Scholar
  • 5 Meggers E. Dussy A. Schäfer T. Giese B. Chem.-Eur. J.  2000,  6:  485 
    Google Scholar
  • 6 Patil SV. Mane RB. Salunkhe MM. Indian J. Chem., Sect. B  1994,  33B:  1 
    Google Scholar
  • 7 Marx A. Erdmann P. Senn M. Körner S. Jungo T. Petretta M. Imwinkelried P. Dussy A. Kulicke KJ. Macko L. Zehnder M. Giese B. Helv. Chim. Acta  1996,  79:  1980 
    CrossrefGoogle Scholar
  • 8 The quantum yield has not been measured. But from structural related ketones one can deduce that the quantum yield should be high (Φ = >0.5): Peukert S. Giese B. J. Org. Chem.  1998,  63:  9045 
    CrossrefGoogle Scholar
  • 9 Meggers E. Kusch D. Spichty M. Wille U. Giese B. Angew. Chem., Int. Ed.  1998,  37:  460 
    Google Scholar
  • 10 Stollwerk J. Gentechnische Methoden   Fischer; Stuttgart: 1991.  p.201 
    Google Scholar