Abstract
The intramolecular chain oxidation of artemisinin was analyzed using the parabolic model. The competition of the mono- and bimolecular peroxy radicals formed from artemisinin was considered. Artemisinin is predominantly oxidized via the intramolecular chain mechanism to form polyatomic hydroperoxides. This results in the situation when, under aerobic conditions, artemisinin is transformed from the monofunctional into polyfunctional initiator with several hydroperoxide groups. The enthalpy was calculated, and the activation energies and rate constants of the intramolecular reactions of the artemisinin peroxy radicals, as well as those of their bimolecular reactions with C-H, S-H, and O-H bonds of biological substrates and their analogs, were calculated in the framework of the parabolic model. A new kinetic scheme for artemisinin oxidation was proposed.
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References
A. Robert, O. Dechy-Cabaret, J. Caelles, B. Meunier, Acc. Chem. Res., 2002, 35, 167.
Y. Wu, Acc. Chem. Res., 2002, 35, 255.
S. R. Meshnick, Int. J. Parasitol., 2002, 32, 1655.
P. M. O’Neill, G. H. Posner, J. Med. Chem., 2004, 47, 2945.
D. L. Klayman, Science, 1985, 228, 1049.
S. L. Solodova, E. T. Denisov, Izv. Akad. Nauk, Ser. Khim., 2006, 1502 [Russ. Chem. Bull., Int. Ed., 2006, 55, 1557].
S. L. Solodova, E. T. Denisov, Kinet. Katal., 2007, 48, 220 [Kinet. Catal., 2007, 48, 204 (Engl. Transl.)].
E. T. Denisov, I. B. Afanas’ev, Oxidation and Antioxidants in Chemistry and Biology, Taylor and Francis, Boca Raton, 2005, 981 pp.
E. T. Denisov, V. E. Tumanov, Usp. Khim., 2005, 74,905 [Russ. Chem. Rev., 2005, 74, 825 (Engl. Transl.)].
V. E. Tumanov, E. T. Denisov, Neftekhimiya, 2003, 43, 406 [Petroleum Chem., 2003, 43, 368 (Engl. Transl.)].
E. T. Denisov, T. G. Denisova, Handbook of Antioxidants, CRC Press, Boca Raton, 2000.
E. T. Denisov, Usp. Khim., 1997, 66, 953 [Russ. Chem. Rev., 1997, 66, 859 (Engl. Transl.)].
E. T. Denisov, T. G. Denisova, Usp. Khim., 2004, 73, 1181 [Russ. Chem. Rev., 2004, 73, 1091 (Engl. Transl.)].
T. G. Denisova, E. T. Denisov, Neftekhimiya, 2004, 44, 278 [Petroleum Chem., 2004, 44, 250 (Engl. Transl.)].
E. T. Denisov, Zh. Fiz. Khim., 1993, 67, 2416 [Russ. J. Phys. Chem., 1993, 67 (Engl. Transl.)].
A. E. Semenchenko, V. M. Solyanikov, E. T. Denisov, Neftekhimiya, 1971, 11, 555 [Petroleum Chem., 1971, 11 (Engl. Transl.)].
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 267–275, February, 2008.
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Solodova, S.L., Denisov, E.T. Intramolecular chain reaction of artemisinin oxidation. Russ Chem Bull 57, 274–282 (2008). https://doi.org/10.1007/s11172-008-0042-7
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DOI: https://doi.org/10.1007/s11172-008-0042-7