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Updated: Jul 18, 2026

Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
Kinetic isotope effects implicate the iron-oxene as the sole oxidant in P450-catalyzed N-dealkylation
Tamara S Dowers1, Dan A Rock, Denise A Rock
1Department of Chemistry, P.O. Box 644630, Washington State University, Pullman, Washington 99164-4630, USA.
Abstract:
Multiple oxidants have been implicated as playing a role in cytochrome P450-mediated oxidations. Herein, we report results on N-dealkylation, one of the most facile reactions mediated by P450 enzymes. We have employed the N-oxides of a series of para-substituted 13C2H2-labeled N,N-dimethylanilines to function as both substrates and surrogate oxygen atom donors for P450cam and P4502E1. Kinetic isotope effect profiles obtained using the N-oxide system were found to closely match the profiles produced using the complete NAD(P)H/NAD(P)-P450 reductase/O2 system. The results are consistent with oxidation occurring solely through an iron-oxene species.
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