Water-Soluble Iron Porphyrin Complex-Catalyzed Epoxidation of Olefins with Hydrogen Peroxide and tert-Butyl Hydroperoxide in Aqueous Solution

Abstract

Catalytic epoxidation of olefins with H2O2 and t-BuOOH has been studied in the presence of a water-soluble iron(III) porphyrin complex, (5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphinato)iron(III) [Fe(TDCPPS)], in buffered aqueous solutions. Epoxides are the predominant products at low pH values, and the formation of the oxide products is found to depend on the pH of the reaction solutions. A high-valent iron(IV) oxo porphyrin cation radical complex is proposed as a reactive intermediate responsible for the olefin epoxidation.

Effect of Temperature and Reaction Time on the Synthesis of Butadiene Monoepoxide Using Iron Complex as an Efficient Catalyst

“…no diepoxide is formed). The proposed mechanism [32,33] for the synthesis of BMO using oxidant peracetic acid and catalyst iron complex is shown in Scheme 2. Table 1 shows the experimental data for the epoxidation of butadiene at different temperature and reaction time.…”

Manganese porphyrin multilayer films assembled on ITO electrodes via zirconium phosphonate chemistry: chemical and electrochemical catalytic oxidation activity

“…Epoxidation in aqueous media has attracted interest because of its biological significance, but studies have been limited by the availability of comparatively few water-soluble catalysts and substrates [37]. However, several reports exist on catalytic oxidation of CBZ in aqueous media using water-soluble metalloporphyrins and various oxidants such as KHSO 5 , H 2 O 2 , m-chloroperbenzoic acid, and NaOCl [29,[38][39][40]. CBZ, first introduced in epoxidation studies by Meunier in 1994 and since then commonly used as a substrate for epoxidation in various aqueous media [29,37], is moderately water soluble.…”

“…We surmise that oxygen transfer from Mn(V)(O) to water occurs competitively with the oxygen transfer to CBZ, i.e., the system generates both hydrogen peroxide and CBZ oxide (scheme 2). The presence of hydrogen peroxide is detrimental to the catalytic system due to its propensity to oxidatively degrade the porphyrin ligand under basic conditions [39,[41][42][43]. Indeed, within 1 h of the start of the film-based electrolysis, porphyrin bleaching was easily observable.…”

Regioselective Biomimetic Oxidation of Etodolac with Iodosylbenzene Catalyzed by Halogenated and Perhalogenated Metalloporphyrins in Dichloromethane.

“…The biomimetic oxidation of selected drugs with monooxygen donors catalyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides (TAPFe(III)Cl) has been studied to understand the drug metabolism as well as to isolate the drug metabolites and reactive intermediates in sufficient amount without the use of experimental animals. [3][4][5][6] The catalytic activity of metalloporphyrins can be increased either by introduction of bulkier substituents at ortho position of the phenyl rings or by substitution of hydrogens by halogens of main porphyrin ring of metalloporphyrins (TAPFe(III)Cl). Herein, we report the biomimetic oxidation of etodolac with iodosylbenzene catalyzed by halogenated and perhalogenated iron(III) porphyrins TAPFe(III)Cl (7a-e) 7) in organic solvents to mimic the reactions of natural cytochrome P450 enzyme.…”