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Asymmetric Sulfoxidation Catalyzed by a Vanadium-Containing Bromoperoxidase
Malin Andersson1, Andrew Willetts, Stig Allenmark
1Department of Chemistry, University of Göteborg, S-41296 Göteborg, Sweden, and Department of Biological Sciences, University of Exeter, Exeter, EX4 4QD, U.K.
The Journal of Organic Chemistry
|October 24, 2001
Summary
Vanadium bromoperoxidase (VBrPO) from Corallina officinalis efficiently oxidizes sulfides to (S)-sulfoxides. Slow hydrogen peroxide addition optimizes yield and stereoselectivity, avoiding overoxidation.
Area of Science:
- Biocatalysis
- Enzymology
- Organic Chemistry
Background:
- Vanadium-containing bromoperoxidases (VBrPO) are enzymes with potential catalytic applications.
- Algal VBrPOs, like that from Corallina officinalis, are increasingly studied for their unique reactivity.
- Stereoselective oxidation of sulfides is a key transformation in synthetic chemistry.
Purpose of the Study:
- To investigate the catalytic activity of Corallina officinalis VBrPO in sulfide oxidation.
- To determine the stereoselectivity and efficiency of the VBrPO-catalyzed reaction.
- To optimize reaction conditions for high yield and enantiomeric excess (ee).
Main Methods:
- Enzymatic oxidation of aromatic bicyclic sulfides using purified VBrPO.
- Optimization of hydrogen peroxide addition rate to control reaction and minimize inhibition.
- Analysis of product enantiomeric excess using chiral chromatography.
Main Results:
- VBrPO catalyzed the stereoselective oxidation of sulfides to (S)-sulfoxides with up to 91% ee.
- Hydrogen peroxide inhibited VBrPO; slow, continuous addition was crucial for high yields.
- The reaction avoided overoxidation to sulfones and exhibited opposite stereochemistry to heme chloroperoxidase (CPO).
Conclusions:
- Corallina officinalis VBrPO is an effective biocatalyst for enantioselective sulfide oxidation.
- Controlled hydrogen peroxide delivery is essential for optimal VBrPO performance.
- This VBrPO offers an alternative stereoselective pathway compared to CPO.