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

Abstract

Alkane hydroxylation by peroxy acids proceeds by a synchronous nonconcerted peroxy oxygen insertion into the C-H bond according to density functional theory. A comparable reaction sequence, initiated by homolytic peroxy bond cleavage, can be formulated for the alkane hydroxylation by the cytochrome P450 hydroperoxo-heme Compound 0. This hydroxylation reaction proceeds by a two-step process because the formed reactive intermediate, Compound II, is significantly stabilized.

Benzaldehyde-mediated selective aerobic polyethylene functionalisation with isolated backbone ketones

“…These two steps strongly resemble the oxygen rebound mechanism, which is an important pathway for the enzymatic hydroxylation of hydrocarbons. Similar metal-free rebound reactions have been previously studied in other peroxy acids 36,43 and oxiranes. 44 The electronic energy component of the reaction barrier TS2B is very low (Δ E ‡ el = 1.9 kcal mol −1 , see ESI section 3.3 for details) and hence the rate of the hydroxyl transfer step can be considered diffusion-controlled.…”

Tetrabutylammonium Iodide Catalyzed Synthesis of Allylic Ester with tert-Butyl Hydroperoxide as an Oxidant

“…3-Chloroperoxybenzoic acid, a known acyloxy radical donor, was also a suitable reaction partner for the transformation (Scheme a). Notably, a tert -butyl perester, from the coupling of the acyloxy and tert -butoxyl radicals, was detected by LC-MS in the reaction mixture (Scheme b).…”

Reaction mechanisms : Part (i) Radical and radical ion reactions

“…As can be gleaned from earlier work presented in this chapter, a good deal of the impetus for studying the mechanism and kinetics of HAT, SPLET, PCET, and related processes is the role they play in biological systems. Radical processes, based upon these mechanisms, have been proposed for enzyme-catalyzed processes, e.g., MAO, 17 p450, [29][30][31] and galactose oxidase, 32 to name a few. PCET has been implicated in photosystem II and other biological processes.…”