D. Wischang et al. / Bioorganic Chemistry 44 (2012) 25–34
33
VBrPO(AnII)
Br
H2O2 / NaBr
+
CO2CH3
CO2CH3
Br
CO2CH3
tBuOH / H2O
N
H
4
N
H
N
H
pH 6.2 / 23°C
5a
5b
35% conv.
22%
9%
Scheme 3. Bromination of methyl pyrrole-2-carboxylate in bromoperoxidase II-catalyzed oxidation [conditions: 63 lmol% of VBrPO(AnII) (34.6 UT), 2.2 equiv. of NaBr, and 2.2
equiv. of H2O2].
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concluded that the product of enzymatic bromide oxidation
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of interest for stimulating discussion on biosynthesis of pyrrole-
derived bromometabolites in nature, but also raises the question
about further functional groups that are receptive for bromofunc-
tionalization in VBrPO-catalyzed oxidations, to obtain a deeper in-
sight into significance role of bromoperoxidases for synthesis of
naturally occurring organobromines. A correlation of this kind is
under current investigation in our laboratories.
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Acknowledgments
This work is dedicated to Professor Dr. Dr. h.c. Gerhard Bring-
mann, on the occasion of his 60th birthday. We thank Prof. Dr. Rita
Bernhardt, Dipl.-Biol. Kerstin Ewen, and Dr. Frank Hannemann for
technical advice in recording CD-spectra, Dr. Jean-Pierre Stockis
and Dipl.-Math. Marion Weber for helpful discussion on numerical
data analysis, and Ms. Astrid Hoppe for technical assistance in
experiments associated with reconstitution of apobromoperoxid-
ases. This work is part of the Ph.D. thesis of D.W. and the diploma
work of M.R.
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