Synthesis of 5-Bromouridine Oligonucleotides by the Reaction of 5-Bromouridine with Tri(imidazol-1-yl)phosphine

Abstract

5-Bromouridine oligonucleotides were synthesized directly from 5-bromouridine by a polycondensation method. The reaction of 5-bromouridine with tri(imidazol-1-yl)phosphine was carried out at a relatively low temperature and the subsequent in situ oxidation of the resulting phosphite oligomer was achieved with iodine and water. 5-Bromouridine oligonucleotides up to a hexamer were obtained in high yields. The phosphodiester linkage of the oligomer consists of both 3′,5′- and 2′,5′-linkages. The interaction of 5-bromouridine oligonucleotides with poly A was investigated.

References

  1. 1

    Y. Lapidot and H. G. Khorana, J. Am. Chem. Soc., 85, 3857 (1963).

  2. 2

    C. Coutsogeorgopoulos and H. G. Khorana, J. Am. Chem. Soc., 86, 2926 (1964).

  3. 3

    E. Ohtsuka, M. Ubasawa, S. Morioka, and M. Ikehara, J. Am. Chem. Soc., 95, 4725 (1973).

  4. 4

    O. B. Straus and J. R. Fresco, J. Am. Chem. Soc., 95, 5025 (1973).

  5. 5

    M. Ikehara, K. Ohsie, and E. Ohtsuka, Tetrahedron Lett., 3677 (1979).

  6. 6

    H. Sawai, T. Shibata, and M. Ohno, Tetrahedron Lett., 4573 (1979).

  7. 7

    H. Sawai, T. Shibata, and M. Ohno, Tetrahedron, 37, 481 (1981).

  8. 8

    T. Shimidzu, K. Yamana, A. Murakami, and K. Nakamichi, Tetrahedron Lett., 2717 (1980).

  9. 9

    T. Shimidzu, K. Yamana, K. Nakamichi, and A. Murakami, J. Chem. Soc., Perkin Trans. 1, 2294 (1981).

  10. 10

    T. Shimidzu, K. Yamana, K. Nakamichi, S. Maikuma, and N. Kanda, Nucleic Acids Res. Symposium Series, No. 11, 89 (1982).

  11. 11

    T. Shimidzu, K. Yamana, A. Murakami, K. Nakamichi, N. Kanda, and S. Maikuma, J. Am. Chem. Soc., submitted.

  12. 12

    W. Hayes, “The Genetics of Bacteria and Their Virus,” Blackwell, Oxford, 1964, p 278.

    Google Scholar 

  13. 13

    A. M. Michelson and C. Mony, Biochim. Biophys. Acta, 149, 107 (1967).

  14. 14

    H. Iwahashi and Y. Kyogoku, J. Am. Chem. Soc., 99, 7761 (1977).

  15. 15

    F. Huchinson, Quart. Rev. Biophys., 6, 201 (1973).

  16. 16

    I. Saito, S. Ito, and T. Matsuura, J. Am. Chem. Soc., 100, 2901 (1978).

  17. 17

    The evidence for the selective phosphorylation of cis-glycols including the 2′,3′-hydroxyl groups of ribo-nucleoside with tri(imidazol-1-yl)phosphine has been appeared: T. Shimidzu, K. Yamana, N. Kanda, and S. Kitagawa, Bull. Chem. Soc. Jpn., 56, 3483 (1983).

  18. 18

    After 5 min oxidation, unreacted iodine was quenched with NaHSO3. The 31P NMR signal due to phosphite 4 was observed at this stage.10 The oxidation of phosphite 4 to phosphate 5 was completed within 30 min.

  19. 19

    Judging from the melting curve in Figure 4, two kinds of the hydrogen-bonded complexes were existed; at 20°C 2-oligo 5-BrU-poly A complex was melted to oligo 5-BrU+oligo 5-BrU-poly A and at 27°C oligo 5-BrU-poly A complex was transformed into oligo 5-BrU+poly A. Tm value of the complex between oligo 5-BrU and poly A was roughly estimated to be 25°C. The Tm value of the complex between poly U and 3′,5′-oligo A was observed slightly higher than that of the complex between poly U and 2′,5′-oligo A.13 Therefore, the Tm value obtained here is probably not so different from that of the poly A–3′,5′-oligo 5-BrU complex.

  20. 20

    T. Ueda, Chem. Pharm. Bull., 8, 455 (1960).

  21. 21

    D. H. Rammer, Y. Lpidot, and H. G. Khorana, J. Am. Chem. Soc., 85, 1989 (1963).

Download references

Author information

Affiliations

Authors

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Shimidzu, T., Yamana, K. Synthesis of 5-Bromouridine Oligonucleotides by the Reaction of 5-Bromouridine with Tri(imidazol-1-yl)phosphine. Polym J 15, 727–732 (1983). https://doi.org/10.1295/polymj.15.727

Download citation

Keywords

  • 5-Bromouridine
  • Tri(imidazol-1-yl)phosphine
  • Polycondensation
  • Oligoribonucleotide
  • 5-Bromouridine Oligonucleotide
  • Phosphodiester Linkage
  • Interaction of 5-Bromouridine Oliogonucleotide

Further reading