PMID: 6882748Jun 21, 1983

Stereoselectivity of chloroperoxidase-dependent halogenation

Biochemistry
K RamakrishnanJ Fisher

Abstract

The stereoselectivity of chloroperoxidase halogenation of four substrates has been examined. Chloroperoxidase catalyzes the bromination, but not chlorination, of racemic 2-exo-methylbicyclo[2.2.1]hept-5-ene-2-endo-carboxylic acid (to the delta-lactone) and racemic bicyclo-[3.2.0]hept-2-en-6-one (to the 2-exo-bromo-3-endo-hydroxy-bromohydrin). These products are obtained in near quantitative yield and are racemic. The circumstances of the bromination strongly suggest that halogenation does not occur at the active site but rather by chloroperoxidase-catalyzed formation of Br2 and its release into solution. The inability of chloroperoxidase to halogenate these two alkenes at its active site most probably derives from a steric exclusion from the active site. The stereoselectivity of two additional substrates that undergo active site chlorination was determined. Methionine is quantitatively converted to a 50:50 ratio of the two methionine sulfoxide diastereomers. 2-Methyl-4-propylcyclopentane-1,3-dione is quantitatively chlorinated to 2-chloro-2-methyl-4-propylcyclopentane-1,3-dione. On the basis of optical rotation and proton nuclear magnetic resonance, this product is present as a 40:60 ratio of the racemic diastereomers. It is co...Continue Reading

References

Nov 1, 1979·The Biochemical Journal·M D Corbett, B R Chipko
Feb 1, 1967·Journal of the American Chemical Society·F S Brown, L P Hager
Jul 1, 1982·Proceedings of the National Academy of Sciences of the United States of America·C W LeeK F Austen
Apr 1, 1981·Canadian Journal of Biochemistry·T AraisoH B Dunford
Aug 1, 1981·Archives of Biochemistry and Biophysics·P L Ashley, B W Griffin

Citations

May 25, 2010·Applied Microbiology and Biotechnology·Martin HofrichterTaina Lundell
May 13, 1998·Acta Physiologica Scandinavica·K SahlinK Söderlund
Jan 1, 1997·Annual Review of Microbiology·A Archelas, R Furstoss
Mar 4, 2005·Proceedings of the National Academy of Sciences of the United States of America·Ellen YehChristopher T Walsh
May 27, 2017·Chemical Communications : Chem Comm·Jia Jia DongFrank Hollmann
Mar 19, 2020·Biomolecular Concepts·Kelath Murali ManojKannan Pakshirajan
Jun 23, 2006·The Journal of Biological Chemistry·Karin KühnelIlme Schlichting
Sep 6, 1996·The Journal of Biological Chemistry·R D LibbyA K Phipps

Related Concepts

Bromine
Chloride Peroxidase
Chlorine
Filamentous fungus
In Vivo NMR Spectroscopy
Ovoperoxidase
Molecular Stereochemistry
Substrate Specificity

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