Molecules 2004, 9
478
There appears to be a remarkably short oxygen-selenium separation in 28, which at 2.68Å is
suggestive of significant contribution of resonance structure 31 to the overall bonding in 28.
Indeed, the O–Se separation in 28 is, to the best of our knowledge, the shortest such interaction
reported, being some 0.04Å shorter than the previous “record” of 2.72Å reported by us recently
[17].
Conclusions
We have presented work toward the preparation of novel pyridine-fused, selenium-containing
antioxidants and anti-inflammatory agents and have demonstrated that, in a model compound,
intramolecular homolytic substitution is an effective method for the preparation of these ring
systems. The unusual reactivity of ethyl 3-oxo-3-(2-(benzylseleno)pyridin-3-yl)butyrate (28) is
attributed to strong non-bonded O–Se interactions that are supported by x-ray analysis
Acknowledgements
Financial support from the Australian Research Council is gratefully acknowledged.
References and Notes
1. (a) May, S. W. Exp. Opin. Invest. Drugs 1999, 8, 1017; (b) May, S.W. Exp. Opin. Invest.
Drugs 2002, 11, 1261; (c) Mugesh, G.; du Mont, W.W.; Sies, H. Chem. Rev. 2001, 101, 2125.
2. Ito, H.; Wang, J.Z.; Shimura, K.; Sakakihara, J.; Ueda, T.; Anticancer Res. 1990, 10, 891.
3. (a) Pollock, S.H.; Herman, H.H.; Fowler, L.C., Edwards, A.S.; Evans, C.O.; May, S.W. J.
Pharm. Exp. Ther. 1988, 246, 227; (b) Koketsu, M.; Ishihara, H.; Hatsu, M. Res. Commun.
Mol. Path. Pharmacol. 1998, 101, 179; (c) Koketsu, M.; Ishihara, H.; Wu, W.; Koji, M.; Saiki,
I. Eur. J. Pharm. Sci. 1999, 9, 157.
4. (a) Arthur, J. R.; McKenzie, R. C.; Beckett, G. J. J. Nutr. 2003, 133, 1457S; (b) Beck, M. A.;
Levander, O. A.; Handy, J. J. Nutr. 2003, 133, 1463S; (c) Jackson, M. J.; Broome, C. S.;
Francis, M. J. Nutr. 2003, 133, 1557S; (d) Neve, J. Curr. Opin. Clin. Nutr. 2002, 5, 659. (e)
Rayman, M. P. The Lancet 2000, 356, 233; (f) Rayman, M. P. Proc. Nutr. Soc. 2002, 61, 203.
5. (a) Arteel, G. E.; Sies, H. Environ. Toxicol. Pharmacol. 2001, 10, 153; (b) Birringer, M.;
Pilawa, S.; Flohe, L. Nat. Prod. Rep. 2002, 19, 693; (c) Nordberg, J.; Arner, E. S. J. Free Rad.
Biol. Med. 2001, 31, 1287; (d) Gamble, S.C.; Wiseman, A. Goldfarb, P.S. J. Chem. Tech.
Biotechnol. 1997, 68, 123; (e) Ursini, F.; Bindoli, A. Chem. Phys. Lipids. 1987, 44, 255.
6. (a) Droge, W. Physiol. Rev. 2002, 82, 47-95; (b) Fridovich, I. Science. 1978, 201, 875.
7. Deby, C.; Goultier, R. Biochem. Biopharm. 1990, 39, 3, 399.
8. (a) Ames, B.N.; Shigenaga, M.K.; Hagen, T.M. Proc. Natl. Acad. Sci. USA. 1993, 90, 7915;
(b) Alexander, R. W. Hypertension. 1995, 25, 155; (c) Niki, E. Chem. Phys. Lipids. 1987, 44,
227.
9. Nordberg, J.; Arner, E. S. J. Free Rad. Biol. Med. 2001, 31, 1287.