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Tunneling Controls the Reaction Pathway in the Deformylation of Aldehydes by a Nonheme Iron(III)-Hydroperoxo Complex: Hydrogen Atom Abstraction versus Nucleophilic Addition

Title
Tunneling Controls the Reaction Pathway in the Deformylation of Aldehydes by a Nonheme Iron(III)-Hydroperoxo Complex: Hydrogen Atom Abstraction versus Nucleophilic Addition
Authors
Bae, Seong HeeLi, Xiao-XiSeo, Mi SookLee, Yong-MinFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우이용민Shunichi Fukuzumi서미숙
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 서미숙scopusscopus
Issue Date
2019
Journal Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN
0002-7863JCR Link
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY vol. 141, no. 19, pp. 7675 - 7679
Publisher
AMER CHEMICAL SOC
Indexed
SCI; SCIE; SCOPUS WOS scopus
Document Type
Article
Abstract
Mononuclear nonheme iron(III)-hydroperoxo intermediates play key roles in biological oxidation reactions. In the present study, we report the highly intriguing reactivity of a nonheme iron(III)-hydroperoxo complex, [(TMC)Fe-III(OOH)(2+) (1), in the deformylation of aldehydes, such as 2-phenylpropionaldehyde (2-PPA) and its derivatives; that is, the reaction pathway of the aldehyde deformylation by 1 varies depending on reaction conditions, such as temperature and substrate. At temperature above 248 K, the aldehyde deformylation occurs predominantly via a nucleophilic addition (NA) pathway. However, as the reaction temperature is lowered, the reaction pathway changes to a hydrogen atom transfer (HAT) pathway. Interestingly, the reaction rate becomes independent of temperature below 233 K with a huge kinetic isotope effect (KIE) value of 93 at 203 K, suggesting that the HAT reaction results from tunneling. In contrast, reactions with a deuterated 2-PPA at the alpha-position and 2-methyl-2-phenylpropionaldehyde proceed exclusively via a NA pathway irrespective of the reaction temperature. We conclude that the bifurcation pathways between NA and HAT result from the tunneling effect in the HAT reaction by 1. To the best of our knowledge, this study reports the first example showing that tunneling plays a significant role in the activation of substrate C-H bonds by a mononuclear nonheme iron(III)-hydroperoxo complex.
DOI
10.1021/jacs.9b02272
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자연과학대학 > 화학·나노과학전공 > Journal papers
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