NDLI: Redox inactive metal ion triggered N-dealkylation by an iron catalyst with dioxygen activation: a lesson from lipoxygenases

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Wang, Yujuan Luo, Nengchao Yin, Guochuan Chen, Zhuqi Wu, Kangbing Zhang, Jisheng
Description	Author Affiliation: Zhang J ( School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Key Laboratory for Large-Format Battery Materials and System, Ministry of Education, Luoyu Road 1037, Wuhan 430074, PR China. gyin@hust.edu.cn.)
Abstract	Utilization of dioxygen as the terminal oxidant at ambient temperature is always a challenge in redox chemistry, because it is hard to oxidize a stable redox metal ion like iron(III) to its high oxidation state to initialize the catalytic cycle. Inspired by the dioxygenation and co-oxidase activity of lipoxygenases, herein, we introduce an alternative protocol to activate the sluggish iron(III) species with non-redox metal ions, which can promote its oxidizing power to facilitate substrate oxidation with dioxygen, thus initializing the catalytic cycle. In oxidations of N,N-dimethylaniline and its analogues, adding $Zn(OTf)_{2}$ to the $[Fe(TPA)Cl_{2}]Cl$ catalyst can trigger the amine oxidation with dioxygen, whereas $[Fe(TPA)Cl_{2}]Cl$ alone is very sluggish. In stoichiometric oxidations, it has also been confirmed that the presence of $Zn(OTf)_{2}$ can apparently improve the electron transfer capability of the $[Fe(TPA)Cl_{2}]Cl$ complex. Experiments using different types of substrates as trapping reagents disclosed that the iron(IV) species does not occur in the catalytic cycle, suggesting that oxidation of amines is initialized by electron transfer rather than hydrogen abstraction. Combined experiments from UV-Vis, high resolution mass spectrometry, electrochemistry, EPR and oxidation kinetics support that the improved electron transfer ability of iron(III) species originates from its interaction with added Lewis acids like $Zn^{2+}$ through a plausible chloride or $OTf^{−}$ bridge, which has promoted the redox potential of iron(III) species. The amine oxidation mechanism was also discussed based on the available data, which resembles the co-oxidase activity of lipoxygenases in oxidative dealkylation of xenobiotic metabolisms where an external electron donor is not essential for dioxygen activation.
ISSN	14779226
Issue Number	21
Volume Number	44
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-06-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Coordination Complexes Chemistry Metals Amines Catalysis Lipoxygenases Oxidation-Reduction Oxygen Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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