Abstract
The Gif family of systems for the selective oxidation of saturated hydrocarbons is briefly described. The mechanism of the reaction is analysed in terms of two intermediates. The first is well characterised as an VFe σ-carbon bond species and the second has been fully identified, at least in the case of cyclohexane, as a hydroperoxide. The utility of dynamic 13C N.M.R. spectroscopy in iron containing systems is demonstrated. Gif type chemistry is closely related to the unusual enzyme methane monooxygenase.
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References
Inter alia A. E. Shilov,’ Activation of Saturated Hydrocarbons by Transition Metal Complexes’ D. Reidel Publishing Co., Dordrecht, 1984.
R. H. Crabtree, Chem. Rev. 1985, 85, 245. B. Meunier, Bull. Soc. Chim. Fr. 1986, 576.’ Activation and Functionalisation of Alkanes’ Ed. C. L. Hill, J. Wiley and Sons, New York, 1989.
M. B. Sponsler, B. H. Weiller, P. O. Stoutland, R. G. Bergman, J. Am. Chem. Soc. 1989, 111, 6841, and references there cited.
T. J. McMurry, J. T. Groves in’ Cytochrome P 450. Structure, Mechanism and Biochemistry’. Ed. P. Ortiz de Montellano, Plenum Press, New York, 1985, Chap. 1.
D. Mansuy, Pure and Appl. Chem. 1987, 59, 759.
J. P. Collman, X. Zhang, R. T. Hembre, J. J. Braumann, J. Am. Chem. Soc. 1990, 112, 5357. J. P. Collman, P. D. Hampton, J. J. Braumann, ibid. 1990, 112, 2977, 2986, and references there cited.
C. Walling. Acc. Chem. Res. 1975, 8, 125.
I. Tabushi, T. Nakajima and K. Seto, Tetrahedron Lett. 1980, 21, 2565.
D. H. R. Barton, M. J. Gastiger, W. B. Motherwell. J. Chem. Soc, Chem. Commun. 1983, 41.
Idem, Ibid, 1983, 731.
D. H. R. Barton, F. Halley, N. Ozbalik, E. Young, G. Balavoine, A Gref, J. Boivin. New J. Chem. 1989, 13, 177.
M. L. Kremer. Int. J. Chem. Kin. 1985, 17, 1299.
C. Sheu, A. Sobkowiak, S. Jeon, D. T. Sawyer. J. Am. Chem. Soc. 1990, 112, 879.
Y. V. Geletii, V. V. Lavrushko, G. V. Lubimova. J. Chem. Soc, Chem. Commun. 1988, 936.
G. Balavoine, D. H. R. Barton, J. Boivin, A. Gref. Tetrahedron Lett. 1990, 31, 659.
See C. Sheu, S. A. Richert, P. Cofré, B. Ross, A. Sobkowiak, D. T. Sawyer, J. R. Kanofsky. J Am. Chem. Soc. 1990, 112, 1936.
E. About-Jaudet, D. H. R. Barton, È. Csuhai, N. Ozbalik. Tetrahedron Lett. 1990, 31, 1657.
G. Balavoine, D. H. R. Barton, A. Gref, I. Lellouche. Tetrahedron Lett. 1990, in press.
D. H. R. Barton, F. Halley, N. Ozbalik, M. Schmitt, E. Young, G. Balavoine. J. Am. Chem. Soc. 1989, 111, 7144.
D. H. R. Barton, È. Csuhai, D. Doller, N. Ozbalik, N. Senglet. Tetrahedron Lett. 1990, 31, 3097.
D. H. R. Barton, È. Csuhai, D. Doller. In preparation.
D. H. R. Barton, È. Csuhai, N. Ozbalik. Tetrahedron 1990, 46, 3743.
G. Balavoine, D. H. R. Barton, J. Boivin, P. LeCoupanec, P. Lelandais. New J. Chem. 1989, 13, 691.
D. H. R. Barton, È. Csuhai, D. Doller. In preparation.
D. H. R. Barton, È. Csuhai, N. Ozbalik. Tetrahedron Lett. 1990, 31, 2817.
D. H. R. Barton, È. Csuhai, D. Doller, N. Ozbalik, G. Balavoine. Proc Natl. Acad. Sci. 1990, 87, 3401.
E. Pretsch, J. Scibl, W. Simon, T. Clerc.’ Spectral Data for Structure Determination of Organic Compounds’. Springer-Verlag, Berlin, 1983.
S. M. Gorun, G. C. Papaefthymiou, R. B. Frankel, S. J. Lippard. J. Am. Chem. Soc. 1987, 109, 3337.
R. W. Saalfrank, A. Stark, M. Bremer, H. U. Hummel. Angew. Chem. Int. Ed. Engl. 1990, 29, 311.
H. R. Williams, H. S. Mosher. J. Am. Chem. Soc. 1954, 76, 2984, 2987.
D. H. R. Barton, È. Csuhai, unpublished observations.
G. Balavoine, D. H. R. Barton, J. Boivin, P. Lecoupanec, P. Lelandais. New J. Chem. 1989, 13, 691.
D. H. R. Barton, S. Bévière and D. Doller. In preparation.
H. Dalton. Adv. Appl. Microbiol. 1980, 26, 71.
J. Colby, H. Dalton. Biochem. J. 1978, 171, 461.
R. C. Prince, G. N. Geoge, J. C. Savas, S. P. Cramer, R. N. Patel. Biochim. Biophys. Acta 1988, 952, 220.
A. Ericson, B. Hedman, K. O. Hodgson, J. Green, H. Dalton, J. G. Bentsen, R. H. Beer, Lippard, S. J. J. Am. Chem. Soc. 1988, 110, 2330.
B. G. Fox, K. K. Sureus, E. Miinck, J. D. Lipscomb. J. Biol. Chem. 1988, 263, 10553.
J. Green, H. Dalton. J. Biol. Chem. 1989, 264, 17698.
D. J. Leak, H. Dalton. Biocatalysis 1987, 1, 23.
D. H. R. Barton, K. W. Lee, W. Mehl, N. Ozbalik, L. Zhang. Tetrahedron 1990, 46, 3753.
H. M. Hanauske-Abel, V. Günzler. J. Theor. Biol. 1982, 94, 421.
U. Schuchardt, V. Mano. Preprints First World Congress and Second European Workshop on New Developments in Selective Oxidation, 1989, D6, 01.
U. Schuchardt, E. V. Spinacé, V. Mano. 4th International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation, Balatonfured, Hungary, 1990.
C. Sheu, A. Sobkowiak, L. Zhang, N. Ozbalik, D. H. R. Barton, D. T. Sawyer. J. Am. Chem. Soc. 1989, 112, 879.
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Barton, D.H.R., Doller, D. (1991). Relevance of Gif Chemistry to Enzyme Mechanisms. In: Kelly, J.W., Baldwin, T.O. (eds) Applications of Enzyme Biotechnology. Industry-University Cooperative Chemistry Program Symposia. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-9235-5_7
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