Horseradish Peroxidase-Catalyzed Enantioselective Reduction of Racemic Hydroperoxy Homoallylic Alcohols:  A Novel Enzymatic Method for the Preparation of Optically Active, Unsaturated Diols and Hydroperoxy Alcohols

Adam, Waldemar; Lazarus, Michael; Hoch, Ute; Korb, Marion N.; Saha‐Möller, Chantu R.; Schreier, Peter

doi:10.1021/jo980028h

Cited by 29 publications

(5 citation statements)

References 19 publications

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“…The accessibility of racemic hydroperoxides, often available in one step from the corresponding alcohol, has spurred the exploration of kinetic and classical resolution strategies to synthesize these compounds. Although enzymatic kinetic resolutions of a few secondary benzylic and α-hydroxy allylic hydroperoxides proceed with excellent selectivities, these systems are limited in substrate scope. To date, all resolutions of tertiary hydroperoxides occur with selectivity factors of less than three …”

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confidence: 99%

Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines: Preparation of Enantioenriched Tertiary Hydroperoxides

2007

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confidence: 99%

Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines: Preparation of Enantioenriched Tertiary Hydroperoxides

2007

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“…the Results). In general, the acceptance of sterically hindered and, particularly, tertiary hydroperoxides by HRP ( , ) and CIP () is poor; thus, this reactivity order of hydroperoxides 1 − 4 reflects presumably the ease of substrate acceptance by the enzymes. Indeed, a control experiment (cf.…”

Section: Discussionmentioning

confidence: 99%

Peroxidase-Catalyzed Oxidative Damage of DNA and 2‘-Deoxyguanosine by Model Compounds of Lipid Hydroperoxides: Involvement of Peroxyl Radicals

Adam

Kurz

Saha‐Möller

2000

Chem. Res. Toxicol.

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The peroxidase-catalyzed decomposition of 3-hydroperoxy-1-butene (1), 2,3-dimethyl-3-hydroperoxy-1-butene (2), tert-butyl hydroperoxide (3), ethyl oleate hydroperoxide 4, and linoleic acid hydroperoxide 5 was applied as a chemical model system to assess whether lipid hydroperoxides may cause DNA damage under peroxidase catalysis. For this purpose, the Coprinus peroxidase (CIP), horseradish peroxidase (HRP), and the physiologically important lactoperoxidase (LP) were tested. Indeed, hydroperoxides 1-5 induce strand breaks in pBR 322 DNA upon peroxidase catalysis. For the nucleoside dG, the enzymatic decomposition of hydroperoxides 1-4 led to significant amounts of 4, 8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine (4-HO-8-oxo-dG) and guanidine-releasing products (GRP), whereas 7, 8-dihydro-8-oxo-2'-deoxyguanosine (8-oxo-dG) was not obtained. In isolated calf thymus DNA, the efficient conversion of the guanine base (Gua) was observed. Peroxyl radicals, which are generated in situ from the hydroperoxides by one-electron oxidation with the peroxidases, are proposed as the active oxidants on the basis of the following experimental facts. (i) Radical scavengers strongly inhibit the guanine oxidation in dG and DNA and strand-break formation in the latter. (ii) EPR spectral studies with 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap confirmed the formation of peroxyl radicals. (iii) The release of molecular oxygen was demonstrated, produced through the disproportionation of peroxyl radicals. The biological relevance of these findings should be seen in the potential role of the combined action of lipid hydroperoxides and peroxidases in damaging cellular DNA through peroxyl radicals.

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“…The (R,R)/(R,S) diols and the (S,S)/(S,R) hydroperoxy alcohols are produced, often with high ees at 50% conversion. 175 6 Oxidation reactions…”

Section: Miscellaneous Reduction Reactionsmentioning

confidence: 99%

Preparative biotransformations

Roberts

2000

J. Chem. Soc., Perkin Trans. 1

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Horseradish Peroxidase-Catalyzed Enantioselective Reduction of Racemic Hydroperoxy Homoallylic Alcohols: A Novel Enzymatic Method for the Preparation of Optically Active, Unsaturated Diols and Hydroperoxy Alcohols

Cited by 29 publications

References 19 publications

Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines: Preparation of Enantioenriched Tertiary Hydroperoxides

Kinetic Resolution of Hydroperoxides with Enantiopure Phosphines: Preparation of Enantioenriched Tertiary Hydroperoxides

Peroxidase-Catalyzed Oxidative Damage of DNA and 2‘-Deoxyguanosine by Model Compounds of Lipid Hydroperoxides: Involvement of Peroxyl Radicals

Preparative biotransformations

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