Mechanisms of hemin-catalyzed oxidations: rearrangements during the epoxidation of trans-cyclooctene

Transition-metal-free microporous and mesoporous catalysts for the epoxidation of cyclooctene with hydrogen peroxide

“…Generally, the epoxidation of cyclooctene is a stereoselective reaction even when using the strained trans-cyclooctene as substrate [32,33]. Nevertheless, when the epoxidation was performed in the presence of zeolite beta or USY, a product assigned to trans-epoxycyclooctane on the basis of the GC-MS analysis was observed.…”

“…Whereas this compound is present in minor amounts with USY (2.6) as the catalyst, its relative amount increases with USY (6) and it becomes the only epoxide product with USY (15) and with both beta zeolites ( Table 1). The formation of the trans-isomer can be explained assuming a carbonation intermediate that allows rotation around the C 1 -C 2 bond of the substrate [33] and a geometrically constrained configuration on the active site inside the zeolite framework that would favour such rotation.…”

Metalloporphyrin-functionalized hexagonal mesoporous silica: Synthesis, structural properties and catalytic activity as cytochrome P450 model

“…In this context, bioinspired oxidation catalysts based on synthetic metalloporphyrins have been extensively studied. These macrocycles are efficient chemical models of P450, since they are able to catalyze the transfer of an oxygen atom in various reactions involving oxidation [2,4,[14][15][16][17][18][19][20][21][22][23].…”

Cytochrome P‐450 model reaction: effects of substitution on the rate of aromatic hydroxylation

“…Although many properties of the enzymes have been mimicked [8,9], the challenge of finding better catalysts for hydroxylation of the inert C-H bond of alkanes and selective oxidation of alkenes and aromatic compounds as well as understanding the mechanism of catalytic oxidation of organic substrates remains an interesting task [10][11][12][13][14]. Most proposed mechanisms involve (PFe IV =O) reactive oxidant but differ in the nature of its reaction with substrates [15][16][17][18][19][20][21][22][23].…”