Epoxidation of alkenes by chloroperoxidase catalysis

Geigert, John; Lee, Terry D.; Dalietos, Demetrios J.; Hirano, David S.; Neidleman, Saul L.

doi:10.1016/0006-291x(86)90507-3

Cited by 67 publications

(21 citation statements)

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“…CPO catalyzes a variety of synthetically useful selective oxidations with hydrogen peroxide without the need for cofactors. The oxidation of indole to oxindole (Corbett and Chipko, 1979), sulfoxidation (Colonna et al, 1992;Colonna et al, 1990;Fu et al, 1992), epoxidation (Allain et al, 1993;Colonna et al, 1993;Dexter et al, 1995;Geigert et al, 1986;Hager and Allain, 1994), hydroxylation of aromatic systems (Miller et al, 1995;Zaks and Dodds, 1995), N-demethylation (Kedderis and Hollenberg, 1984;Kedderis and Hollenberg, 1983;Kedderis et al, 1980), the oxidation of alcohols to aldehydes (Geigert et al, 1983), and halogenation reactions (Franssen, 1994) have been performed, generally with high selectivity. CPO also retains its activity in aqueous t-butyl alcohol media, which is an advantage with non-polar organic substrates (Deurzen et al, 1994).…”

Section: Introductionmentioning

confidence: 98%

Improvement of the total turnover number and space-time yield for chloroperoxidase catalyzed oxidation

Seelbach

Deurzen

Rantwijk

et al. 1997

Biotechnol. Bioeng.

110

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Section: Introductionmentioning

confidence: 98%

Improvement of the total turnover number and space-time yield for chloroperoxidase catalyzed oxidation

Seelbach

Deurzen

Rantwijk

et al. 1997

Biotechnol. Bioeng.

110

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“…nation of a variety of organic substrates (peroxidatic and halogenation reactions), CPO also catalyzes the dismutation of hydrogen peroxide (catalatic reaction), chlorination and bromination reactions, and some cytochrome P 450 monooxygenase reactions (2)(3)(4)(5)(6)(7)(8). The mechanisms of CPO-catalyzed chlorination reactions have been studied for more than 30 years; however, there is still considerable controversy over how the chlorine becomes attached to the organic substrate.…”

mentioning

confidence: 99%

Quantitating Direct Chlorine Transfer from Enzyme to Substrate in Chloroperoxidase-catalyzed Reactions

Libby

Beachy

Phipps

1996

Journal of Biological Chemistry

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Substrate competition methods that were previously used to quantitate the involvement of free Cl 2 in the chloride-dependent peroxidatic reactions catalyzed by chloroperoxidase (CPO) (Libby, R. D., Shedd, A. L., Phipps, K. A., Beachy, T. M., and Gerstberger, S. M., (1992) J. Biol. Chem. 267, 1769 -1775) are extended to CPO-catalyzed halogenation reactions. Relative substrate specificities of halogen acceptor substrates (RHs) antipyrine (ap), NADH, 2-chlorodimedone (2cd), and barbituric acid (ba) are compared with previously studied peroxidatic substrates catechol (cat) and 2,4,6-trimethylphenol (tmp) in their reactions with the CPO-H 2 O 2 -Cl system versus the hypochlorite-Cl system. Studies were carried out at pH 2.75 over a chloride concentration range of 1-100 mM and at pH 4.80 over a chloride concentration range of 100 -400 mM. Competition studies involved successive pairwise comparisons of substrates of increasing enzyme specificity. The orders of specificities, ba > 2cd > ap > cat > tmp at pH 2.75 and ba > 2cd > NADH > ap > cat > tmp at pH 4.80, are the same for both the CPO-H 2 O 2 -Cl and hypochlorite-Cl systems. However, the magnitudes of the specificities are different between the two systems. In all comparisons except ap versus cat, the specificity of the CPO-H 2 O 2 -Cl system toward the preferred substrate is higher than that of the hypochlorite-Cl system. Quantitative comparisons between specificities of CPO-H 2 O 2 -Cl and hypochlorite-Cl systems indicate that at least 98% of the CPO-catalyzed halogenation reactions of ba, 2cd, NADH, and ap occur by mechanisms in which the substrate reacts directly with the enzyme. Thus, less than 2% of any of the CPO reactions could possibly involve a free oxidized halogen intermediate. All data are consistent with a mechanism in which RH binds to the CPO chlorinating intermediate (EOCl), and the chlorine atom is transferred directly from EOCl to RH. Further, the results indicate that any halogenation substrate with a higher CPO specificity than ap must also undergo direct chlorine transfer from the enzyme.These results underscore the critical need for quantitative kinetic evidence in establishing the extent of involvement of any potential reaction intermediate. 269, 7950 -7956).Recently we reported the first direct kinetic evidence for the involvement of a free oxidized chlorine intermediate, Cl 2 , in a reaction catalyzed by chloroperoxidase (chloride:hydrogen peroxide oxidoreductase, EC 1.11.1.10) (1). CPO 1 is a very versatile enzyme. In addition to catalyzing reactions characteristic of peroxidases, hydrogen peroxide-supported oxidation, and iodi-* This work was supported by NIGMS, National Institutes of Health, Grant 7 R15 GM42078-02. The costs of publication of this article were defrayed in part by the payment of page charges. This article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. Section 1734 solely to indicate this fact.‡ To whom correspondence should be addressed.1 The abbreviations used are: CPO, chloroperoxidase; t...

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“…In the mono-oxygenase mode, Cpd I reacts directly with the substrate in a two-electron process, this is the underlying mechanism for a variety of reactions that CPO catalyzes, such as mono-oxygenation (Geigert, Lee et al 1986;Ortiz de Montellano, Choe et al 1987;Horner, Mouesca et al 2007), hydroxylation (Miller, Tschirret-Guth et al 1995), sulfoxidation (Casella, Gullotti et al 1992) and demethylation (Kedderis, Koop et al 1980;Kedderis and Hollenberg 1984).…”

Section: Chloroperoxidase Reaction Mechanismmentioning

confidence: 99%

“…The reaction mixture was extracted with 300 µL of isooctane. The HPLC analysis of the extracted organic phase was conducted on a Pirkle Concept WhelkO-1-SS column (2% isopropyl alcohol in hexane, 1 mL/min, and UV detector at 214 nm) to determine the yield of the reaction and the enantiomeric excess of epoxides (Geigert, Lee et al 1986). …”

Section: Activity Assaysmentioning

confidence: 99%

“…In addition, CPO has the potential to catalyze the synthesis of a wide range of chiral or prochiral products. Chloroperoxidase can catalyze many reactions that are important in synthesis such as sulfoxidation (Silverstein and Hager 1974;Doerge 1986), hydroxylation (Miller, Tschirret-Guth et al 1995) and epoxidation (Geigert, Lee et al 1986), enantioselectivly and in high yield (Casella, Poli et al 1994;Lakner and Hager 1996), such as the epoxidation of olefins (Ortiz de Montellano, Choe et al 1987), where traditional peroxidases have failed. Other reactions such as N-demethylation (Kedderis, Koop et al 1980) and dehalogenation (Osborne, Raner et al 2006) are also possible.…”

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confidence: 99%

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Characterization of Recombinant Chloroperoxidase, and F103A and C29H/C79H/C87H Mutants

Zheng¹

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Epoxidation of alkenes by chloroperoxidase catalysis

Cited by 67 publications

References 10 publications

Improvement of the total turnover number and space-time yield for chloroperoxidase catalyzed oxidation

Improvement of the total turnover number and space-time yield for chloroperoxidase catalyzed oxidation

Quantitating Direct Chlorine Transfer from Enzyme to Substrate in Chloroperoxidase-catalyzed Reactions

Characterization of Recombinant Chloroperoxidase, and F103A and C29H/C79H/C87H Mutants

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