9236
G. V. Nizova et al. / Tetrahedron 58 (2002) 9231–9237
II
The interaction of Fe with H O possibly begins from the
2
10. Yoshizawa, K.; Ohta, T.; Yamabe, T.; Hoffmann, R. J. Am.
Chem. Soc. 1997, 119, 12311–12321.
2
formation of a hydroperoxy derivative similar to that
proposed for the hemerythrin oxidized form (see Scheme
). Apparently, certain amino acids added to the reaction
11. van der Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54,
12985–13011.
1
mixture play a very important role in this stage, because
addition of these amino acids dramatically enhances the
oxidation efficiency. We can assume that an amino acid
facilitates the proton transfer between the coordinated H O
12. Fontecave, M.; M e´ nage, S.; Duboc-Toia, C. Coord. Chem.
Rev. 1998, 178–180, 1555–1572.
13. Willems, J.-P.; Valentine, A. M.; Gurbiel, R.; Lippard, S. J.;
Hoffman, B. M. J. Am. Chem. Soc. 1998, 120, 9410–9416.
14. Deeth, R. J.; Dalton, H. JBIC 1998, 3, 302–306, and
subsequent papers in this issue.
2
2
molecule and ligands at iron centers to produce the
Fe–OOH fragment (see a discussion of such type processes
4
8–50
in vanadium-PCA-catalyzed oxidations
). Furthermore,
15. Valentine, A. M.; Stahl, S. S.; Lippard, S. J. J. Am. Chem. Soc.
hydroxyl radical attacks an alkane molecule and the alkyl
radical thus formed adds rapidly an oxygen molecule
affording corresponding alkyl peroxy radical:
1
999, 121, 3876–3887.
1
6. Shilov, A. E.; Shul’pin, G. B. Oxidation in Living Cells and its
Chemical Models. Activation and Catalytic Reactions of
Saturated Hydrocarbons in the Presence of Metal Complexes;
Kluwer Academic: Dordrecht, 2000; Chapter XI, pp 466–
522.
z
z
RH þ HO ¼ R þ H O
2
z
z
R þ O ¼ ROO
2
1
1
7. Costas, M.; Chen, K.; Que, Jr. L. Coord. Chem. Rev. 2000,
2
This radical can be reduced by one of the two iron(II)
centers in the dinuclear complex and, after addition of a
proton, a molecule of the alkyl hydroperoxide is formed:
00–202, 517–544.
8. Solomon, E. I.; Brunold, T. C.; Davis, M. I.; Kemsley, J. N.;
Lee, S.-K.; Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S.;
Zhou, J. Chem. Rev. 2000, 100, 235–349.
z
II
II
2
III
II
ROO þ Fe –Fe ¼ ROO þ Fe –Fe
1
9. Solomon, E. I. Inorg. Chem. 2001, 40, 3656–3669.
20. Lee, D.; Lippard, S. J. Inorg. Chem. 2002, 41, 827–837.
2
þ
ROO þ H ¼ ROOH
2
2
2
1. Nishida, Y.; Yamada, K. J. Chem. Soc., Dalton Trans. 1990,
3
We realize that the scheme described above is a very
simplified sequence of reactions which operate in our
system. One can assume that in addition or instead of
hydroxyl radicals, metal-containing oxygen-centered
radicals are species which abstract hydrogen atoms from
alkanes to produce corresponding alkyl radicals. In any
case, nevertheless, activation of inert C–H bonds in alkanes
proceeds with low selectivity via attack of strong oxygen-
centered radicals. Such a mechanism is postulated for the
alkane oxidations by MMO and, thus the system described
in the present paper can be considered as a structural and
functional model of MMO.
639–3641.
2. Kitajima, N.; Ito, M.; Fukui, H.; Moro-oka, Y. J. Chem. Soc.,
Chem. Commun. 1991, 102–104.
3. Fish, R. H.; Konings, M. S.; Oberhausen, K. J.; Fong, R. H.;
Yu, W. M.; Christou, G.; Vincent, J. B.; Coggin, D. K.;
Buchanan, R. M. Inorg. Chem. 1991, 30, 3002–3006.
4. Belova, V. S.; Gimanova, I. M.; Stepanova, M. L.; Khenkin,
A. M.; Shilov, A. E. Doklady Akad. Nauk SSSR 1991, 316,
2
6
53–657.
2
2
2
2
5. Kulikova, V. S.; Gritsenko, O. N.; Shteinman, A. A.
Mendeleev Commun. 1996, 119–120.
6. M e´ nage, S.; Galey, J.-B.; Hussler, G.; Seit e´ , M.; Fontecave, M.
Angew. Chem., Int. Ed. Engl. 1996, 35, 2353–2355.
7. Ito, S.; Okuno, T.; Itoh, H.; Ohba, S.; Matsushima, H.; Tokii,
T.; Nishida, Y. Z. Naturforsch. 1997, 52b, 719–727.
Acknowledgements
8. Knops-Gerrits, P. P.; Dick, S.; Weiss, A.; Genet, M.; Rouxhet,
P.; Li, X. Y.; Jacobs, P. A. In Third World Congress on
Oxidation Catalysis; Grasselli, R. K., Oyama, S. T., Gaffney,
A. M., Lyons, J. E., Eds.; Elsevier: Amsterdam, 1997; pp
We thank the Russian Basic Research Foundation (grant No.
9
8-03-32015a) and the Swiss National Science Foundation
grant No. 20-64832.01) for support. The authors are
(
indebted to Dr Yuriy N. Kozlov for useful discussions.
1
061–1070.
2
3
9. Duboc-Toia, C.; M e´ nage, S.; Lambeaux, C.; Fontecave, M.
Tetrahedron Lett. 1997, 38, 3727–3730.
0. M e´ nage, S.; Galey, J.-B.; Dumats, J.; Hussler, G.; Seit e´ , M.;
Luneau, I. G.; Chottard, G.; Fontecave, M. J. Am. Chem. Soc.
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