TY - JOUR
T1 - Substrate activation by iron superoxo intermediates
AU - van der Donk, Wilfred A.
AU - Krebs, Carsten
AU - Bollinger, J. Martin
N1 - Funding Information:
This work has been supported by the National Institutes of Health (GM77596 to WAV and GM69657 and DK074641 to JMB and CK), the National Science Foundation (MCB-0642058 and CHE-724084 to CK and JMB), the Petroleum Research Fund of the American Chemical Society (47214-AC3 to JMB and CK). The authors thank Megan Matthews (Penn State) and Satish Nair (UIUC) for assistance with preparation of Figure 2 .
PY - 2010/12
Y1 - 2010/12
N2 - A growing number of non-heme-iron oxygenases and oxidases catalyze reactions for which the well-established mechanistic paradigm involving a single C-H-bond-cleaving intermediate of the Fe(IV)-oxo (ferryl) type [1•] is insufficient to explain the chemistry. It is becoming clear that, in several of these cases, Fe(III)-superoxide complexes formed by simple addition of O2 to the reduced [Fe(II)] cofactor initiate substrate oxidation by abstracting hydrogen [2,3•]. This substrate-oxidizing entry route into high-valent-iron intermediates makes possible an array of complex and elegant oxidation reactions without the consumption of valuable reducing equivalents. Examples of this novel mechanistic strategy are discussed with the goal of bringing forth unifying principles.
AB - A growing number of non-heme-iron oxygenases and oxidases catalyze reactions for which the well-established mechanistic paradigm involving a single C-H-bond-cleaving intermediate of the Fe(IV)-oxo (ferryl) type [1•] is insufficient to explain the chemistry. It is becoming clear that, in several of these cases, Fe(III)-superoxide complexes formed by simple addition of O2 to the reduced [Fe(II)] cofactor initiate substrate oxidation by abstracting hydrogen [2,3•]. This substrate-oxidizing entry route into high-valent-iron intermediates makes possible an array of complex and elegant oxidation reactions without the consumption of valuable reducing equivalents. Examples of this novel mechanistic strategy are discussed with the goal of bringing forth unifying principles.
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U2 - 10.1016/j.sbi.2010.08.005
DO - 10.1016/j.sbi.2010.08.005
M3 - Review article
C2 - 20951572
AN - SCOPUS:78649675114
SN - 0959-440X
VL - 20
SP - 673
EP - 683
JO - Current Opinion in Structural Biology
JF - Current Opinion in Structural Biology
IS - 6
ER -