Abstract
Four chiral π-phenolato dinuclear (VO)2, Cr2, Mn2, and Fe2 complexes with a phenolic ligand bearing two L-phenylanalines as complexing arms have been synthesized and characterized. Asymmetric epoxidations of styrene with these complexes as chiral models of methane monooxygenase (MMO) and iodosylbenzene as an oxygen atom donor have been studied. The results reveal that the Mn2, complex catalyzes asymmetric epoxidation of styrene with the formation of R-(+)-styrene oxide in 42.8% e. e. Contrarily, the (VO)2 analogue complex gives S-(-)-styrene oxide in 19.2% e.e. EPR investigations suggest that the catalyzed epoxidations with the Mn2, Cr2 and Fe2 complexes proceed via high-valent oxometal intermediates; while in the case of the (VO)2 complex as catalyst, the epoxidation proceeds by a pathway that involves a complex of metal-iodine ligand. The catalytic activities of the complexes decrease in a sequence of Mn2>Cr2>(VO)2> Fe2.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Aitken, R. A., Kilenyi, S. N.,Asymmetric Synthesis, New York: Blackie Academic & Professional, 1992.
Liu, A. M., Isolation practice and enzymatic reaction of a methane monooxygenase (in Chinese),Ph. D. Thesis, Lanzhou Institute of Chemical Physics, CAS, Lanzhou, 1991.
Groves, J. T., Myers, R. S., Catalytic asymmetric epoxidations with chiral iron porphyrins,J. Am. Chem. Soc., 1983, 105:5791.
Jфrgensen, K. A., Schioett, B., Larsen, E., Manganese-salicylidene-amino acid complexes as catalysts for alkene epoxidation,J. Chem. Res. (M), 1989, 1673.
Que, L. Jr., True, A. E., Dinuclear iron-and manganase-oxo sites in biology,Prog. Inorg. Chem, 1990, 38:98.
Nakamoto, K.,Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed., New York: John Wiley & Sons, 1986.
Kasuga, K., Nagahara, T., Yamamoto, Y., The color isomerism of oxovanadium(IV) complexes with tetradentate Schiff base,Bull. Chem. Soc. Jpn., 1982, 55:2665.
Kolawole, G. A., Patel, K. S., The stereochemistry of oxovanadium (IV) complexes derived from salicylaldehyde and polyethylenediamines,J. Chem. Soc., Dalton Trans., 1981, (6):1241.
Liu, S. H., Wang, D. H., Pan, C. H.,X-ray Photoelectron Spectroscopy Analysis (in Chinese), Beijing: Science Press, 1988.
Rodgers, K. R., Goff, H. M., Generation and characterization of highly relative oxo-transfer intermediates and related species derived from (tetraarylporphinato) manganase(III) complexes,J. Am. Chem. Soc., 1988, 110:7049.
Upadhyay, M. J., Trivedi, B. M., Bhattacharya, P. K. et al., Synthesis of binuclear complexes of manganese (II), chromium(III), and iron(III) with 1, 3-bis[1-(pyridin-2-yl) ethylideneamino]propan-2-ol and study of their use as catalyst for epoxidation of alkenes,J. Mol. Catal., 1992, 73:287.
YOU, X. Z.,Introduction for Structural Analysis (in Chinese), Beijing: Science Press, 1980, 417–418.
Nam, W., Valentine, J. S., Zinc(II) complexes and alumium(III) porphyrin complexes catalyze the epoxidation of olefins by iodosylbenzene,J. Am. Chem. Soc., 1990, 112:4977.
Kitajima, N., Fukui, H., Moro-oka, Y., A model for methane monooxygenase: dioxygen oxidation of alkanes by use of a π-oxo binuclear iron complex,J. Chem. Soc., Chem. Commun., 1988, (7):485.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Wei, J., Yu, X. & Jin, D. Chiral model complexes for methane monooxygenase and their asymmetric catalysis of styrene epoxidation. Sc. China Ser. B-Chem. 41, 247–254 (1998). https://doi.org/10.1007/BF02879703
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF02879703