Summary
The manganese and iron complexes of the bis-pocket porphyrin (5,10,15,20-tetrakis- (2′4′6′-triphenyl)phenylporphyrin, H2TTPPP) are shown to be shape selective catalysts for the hydroxylation of alkanes and the epoxidation of nonconjugated dienes with a wide variety of oxidants. The selectivities are independent of the choice of oxidant, demonstrating that the mechanism of epoxidation is very similar for all oxidant systems studied. The selectivities for terminal hydroxylation of n-alkanes are very similar to those for terminal epoxidation of 1,4-dienes and are dominated by the steric demands of the metalloporphyrin catalyst. There is, however, a dramatic diminution in selectivity for iron versus manganese. This means that both metals cannot be generating a common metalloxetane intermediate. The selectivities observed for MnTTPPP(OAc) for both 4-vinyl-1-cyclohexene and limonene are very high and approach those of limonene-induced ctyochrome P450.
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References
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Suslick, K.S., Cook, B.R. (1990). Shape Selective Oxidation as a Mechanistic Probe. In: Atwood, J.L. (eds) Inclusion Phenomena and Molecular Recognition. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-0603-0_21
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