Journal article
One-electron oxidation of vindoline and 16-O-acetylvindoline catalyzed by peroxidase
Journal of medicinal chemistry, Vol.28(5), pp.629-633
1985
DOI: 10.1021/jm50001a016
PMID: 3989822
Abstract
The mechanism of oxidation of the alkaloids vindoline (1) and 16-O-acetylvindoline (1a) was examined by use of the reversible redox cycle of horseradish peroxidase (HRP). Oxidation of 1 by HRP resulted in the formation of the enamine dimer 5. The highly reactive radical cation species 2 is an implied intermediate in the oxidation process. During the reaction, HRP-I was reduced to HRP-II by abstraction of an electron from vindoline. The vindoline radical thus formed eliminates a second electron and a proton to produce a highly reactive iminium derivative which undergoes intramolecular etherification and dimerization. Oxidation of 16-O-acetylvindoline (1a) by HRP-I results in the production of an iminium derivative 3a concomitant with the formation of HRP-II. The iminium 3a was isolated and characterized and was converted into monodeuterated la by reduction with NaBD4. The stoichiometry (HRP-II)/(substrate) was determined to be 4.77 ± 0.17 for vindoline and 2.27 ± 0.20 for 16-O-acetylvindoline. The enamine dimer also reduced HRP-I to form HRP-II, but the stoichiometry of this reaction was variable. © 1985, American Chemical Society. All rights reserved.
Details
- Title: Subtitle
- One-electron oxidation of vindoline and 16-O-acetylvindoline catalyzed by peroxidase
- Creators
- F Sima Sariaslani - Univ. Iowa, coll. pharmacyM. W Duffel - Univ. Iowa, coll. pharmacyJ. P Rosazza - Univ. Iowa, coll. pharmacy
- Resource Type
- Journal article
- Publication Details
- Journal of medicinal chemistry, Vol.28(5), pp.629-633
- Publisher
- American Chemical Society
- DOI
- 10.1021/jm50001a016
- PMID
- 3989822
- ISSN
- 0022-2623
- eISSN
- 1520-4804
- Language
- English
- Date published
- 1985
- Academic Unit
- Pharmacy; Pharmaceutical Sciences and Experimental Therapeutics; Medicinal and Natural Products Chemistry
- Record Identifier
- 9984303163802771
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