Selective functionalization of hydrocarbons. 6. Mechanistic and preparative studies on the regio- and stereoselective paraffin hydroxylation with peracids

Half‐Sandwich Scorpionate Vanadium, Iron and Copper Complexes: Synthesis and Application in the Catalytic Peroxidative Oxidation of Cyclohexane under Mild Conditions

“…In fact, M n À OOH species, which have also been invoked in some peroxidative alkane oxidations systems, can undergo, in principle, any of the following further reactions: [10,26] (i) attack at the alkane (RH), thus acting as a metalbased oxidant, to yield The promoting effect of 3-chloroperoxybenzoic acid, 3-ClC 6 H 4 C(=O)OOH, can be associated to the metal-assisted formation of the reactive hydroxyl radical (upon homolytic scission of the O À O 712 asc.wiley-vch.de bond), [27,28] of an oxo-metal (M=O) active species (by heterolytic O À O bond cleavage) [27,29] or of the reactive acylperoxy radical 3-ClC 6 H 4 C(=O)OOC [29,30] (which can oxygenate the alkane RH to give the alcohol ROH and the corresponding acyloxy radical 3-ClC 6 H 4 COOC).…”

Alkane Hydroxylation by Peroxy Acids: A Comparison with the Cytochrome P450 Hydroxylation

“…[1][2][3][4][5][6][7][8] Nature instead makes use of the catalytic function of the iron-heme prosthetic in oxidoreductase enzymes, e.g., catalases, peroxidases, and heme-thiolate proteins. Are there similarities between the two types of oxidations?…”

Synthesis of oxazirino[2,3-a][1,5]benzodiazepines by oxidation of 1H-1,5-benzodiazepines withm-chloroperbenzoic acid (MCPBA)

“…Based on the results published in the literature [22,23] and our experimental results, a possible mechanism of 1H-1,5-benzodiazepine hydroxylation could be presumed to be a radical procedure (Scheme 2). At first, the peracid MCPBA decomposes to yield a carboxy radical and a hydroxy radical.…”