ESR evidence for a heterolytic C,O-bond cleavage in models of 4'-DNA radicals

Tetrahedron Letters

Volumn 38, Issue 20, 1997, Pages 3507-3510

  Peukert, Stefan ^a   Batra, Rohit ^a   Giese, Bernd ^a  

^a UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; DNA CLEAVAGE; ELECTRON SPIN RESONANCE; IN VITRO STUDY; PHOTOLYSIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0030994177     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00676-X     Document Type: Article

References (15)

1. For recent reviews, see: J. Stubbe, J. W. Kozarich, W. Wu, D. E. Vanderwall, Acc. Chem. Res. 1996, 29, 322. P. C. Dedon, I. H. Goldberg, Chem. Res. Toxicol. 1992, 5, 311.
2. For recent reviews, see: J. Stubbe, J. W. Kozarich, W. Wu, D. E. Vanderwall, Acc. Chem. Res. 1996, 29, 322. P. C. Dedon, I. H. Goldberg, Chem. Res. Toxicol. 1992, 5, 311.
3. B. Giese, A. Dussy, C. Elie, P. Erdmann, U. Schwittter, Angew. Chem. Int. Ed. Engl. 1994, 33, 1861. D. Schulte-Frohlinde, CHIUZ, 1990, 37, 1.
4. B. Giese, A. Dussy, C. Elie, P. Erdmann, U. Schwittter, Angew. Chem. Int. Ed. Engl. 1994, 33, 1861. D. Schulte-Frohlinde, CHIUZ, 1990, 37, 1.
5. We tried to observe ESR spectra starting from the precusors 4 and 5 in several solvents, at various temperatures, with the addition of radical starters, or with light All these experiments were unsuccessful. To our knowledge, ESR spectra of deoxyriboses with the radical center at 4-C have not been observed until now.
6. Compound 6 is the enantiomer of the phenyl analogues of 4 and 5. We used 6 because it can be synthesized easily: S. Peukert, B. Giese, Tetrahedron Lett. 1996, 37, 4365.
7. 2-free benzene) in suprasil quartz tubes at 7°C. In addition to the radicals 7a and 9, the ESR spectra showed the tert-butyl radical. These lines were substracted in order to obtain the ESR spectra of radicals 7a and 9 in Figures 2 and 3. The g-values of radicals 7a and 9 are 2.0030.
8. R. Batra, B. Giese, M. Spichty, G. Geschcid, K. N. Houk, J. Phys. Chem. 1996, 100, 18371. This procedure proved to be a reliable method for obtaining hyperfine coupling constants of organic radicals.
9. The axial orientation of the C,O-bond at 3-C can be explained by the anomeric effect of α,β-dioxyalkyl radicals: J. Dupuis, B. Giese, D. Rüegge, H. Fischer, H.-G. Korth, R. Sustmann, Angew. Chem. Int. Ed. Engl. 1984, 23, 896. H. G. Korth, R. Sustmann, J. Dupuis, B. Giese, J. Chem. Soc. Perkin Trans. II 1986, 1453.
10. The axial orientation of the C,O-bond at 3-C can be explained by the anomeric effect of α,β-dioxyalkyl radicals: J. Dupuis, B. Giese, D. Rüegge, H. Fischer, H.-G. Korth, R. Sustmann, Angew. Chem. Int. Ed. Engl. 1984, 23, 896. H. G. Korth, R. Sustmann, J. Dupuis, B. Giese, J. Chem. Soc. Perkin Trans. II 1986, 1453.
11. B. Giese, X. Beyrich-Graf, J. Burger, C. Kesselheim, M. Senn, T. Schäfer, Angew. Chem. Int. Ed. Engl. 1993, 32, 1742.
12. L. Lunazzi, G. Placucci, L. Grossi, Tetrahedron 1983, 39, 159.
13. Some recent publications: A. Albini, M. Mella, M. Freccero, Tetrahedron 1994, 50, 575. A. Faucitano, A. Buttafava, F. Martinotti, R. Sustmann, H.-G. Korth, Tetrahedron Lett. 1992, 33, 2223.
14. Some recent publications: A. Albini, M. Mella, M. Freccero, Tetrahedron 1994, 50, 575. A. Faucitano, A. Buttafava, F. Martinotti, R. Sustmann, H.-G. Korth, Tetrahedron Lett. 1992, 33, 2223.
15. D. R. Arnold, S.A. Mines, Can. J. Chem. 1989, 67, 689.