30
D. CarvalhoDa-Silva et al. / Applied Catalysis A: General 408 (2011) 25–30
by which the -bromination affects the catalytic activity depends
on the choice of oxidant. Better oxidation selectivity for CBZ-EP
was achieved by using t-BuOOH and H2O2 as oxygen donor: 100%
and ∼94% of selectivity, respectively. While no direct evidence is
available to explain the pathway of diol formation in these par-
ticular systems, further experiments are being undertaken in our
laboratory to elucidate this mechanism.
The results showed that metalloporphyrins with both bulky
and electron-withdrawing substituents, such as bromine, in the -
pyrrole positions of the porphyrin ring result in robust catalysts,
but the steric hindrance of substituents hamper the approach of
the oxidant and substrate, resulting in lower catalytic performance,
as observed for the octa-brominated manganese porphyrin. There-
fore, it is important to consider a balance between the effects of the
catalytic species activation and the steric hindrance in the design
of a good biomimetic model of cytochrome P450.
The recent uses of PhI(OAc)2 as oxidant and the absence of the
operating mechanism of this oxidant suggest the need for a more
detailed investigation. Further studies are underway in our labora-
tory in order to identify the intermediate species acting with this
oxidant.
The results showed in this work indicated that these manganese
porphyrins are promising bioinspired catalysts for the oxidation of
other drugs.
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