Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases

Kato, Shunsuke; Nishiwaki, Haruka; Endo, Keiji et al.

Angewandte Chemie - International Edition, 2025, e202511590

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Identifier to cite or link to this item: https://hdl.handle.net/11094/102955

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Title
Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases
Creator
NRID
1000060909125 1000060909125
ORCID
0009-0003-6824-612X 0009-0003-6824-612X
researchmap permalink
s_kato_chem s_kato_chem
Scopus Author ID
57195564115 57195564115
CreatorName
Kato, Shunsuke
CreatorName
Nishiwaki, Haruka
CreatorName
Endo, Keiji
NRID
1000020222226 1000020222226
ORCID
0000-0002-2215-935X 0000-0002-2215-935X
researchmap permalink
20190602_Sun 20190602_Sun
Scopus Author ID
55735983400 55735983400
CreatorName
Hayashi, Takashi
Subject
Aldoxime dehydratase
Biocatalysis
Hemoproteins
Iminyl radicals
Oximes
Description
Kato S., Nishiwaki H., Endo K., et al. Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases. Angewandte Chemie - International Edition, e202511590 (2025); https://doi.org/10.1002/anie.202511590.
Abstract
The iminyl radical is a distinctive N-centered radical which serves as a versatile synthon in preparation of nitrogen-containing compounds. In principle, iminyl radicals can be directly generated by single electron reduction of oximes through elimination of OH group. However, due to the low reactivity of the oxime N─OH bonds, direct conversion of the oximes does not proceed efficiently, thereby enforcing chemical activation of the oxime OH group which results in the formation of stoichiometric by-products. To overcome this problem, we are developing a new biocatalytic system using aldoxime dehydratases. Through a series of enzyme screenings, we identified an aldoxime dehydratase from N. simplex (NsOxd) which is capable of catalyzing iminyl radical-mediated ring-opening reactions. Notably, NsOxd efficiently converts the “non-activated” 2-phenylcyclobutanone oxime within 10 min under ambient conditions and quantitatively produces the corresponding γ-sulfinylated nitrile in >95% yield. This enzyme activity is even faster than that of previously-reported chemo-catalysts. Furthermore, evaluation of the scope of potential substrates indicates that NsOxd has a versatile N─O bond cleaving activity which efficiently generates iminyl radicals from various “non-activated” oximes. These findings highlight the utility of aldoxime dehydratases for managing the reactivity of “non-activated” oximes and for achieving challenging iminyl radical-mediated catalytic reactions.
Publisher
John Wiley and Sons Inc
Source Title
Angewandte Chemie - International Edition
Page
e202511590
Date of Issued
2025-08-21
Language
English
Handle URL
https://hdl.handle.net/11094/102955
PISSN
14337851
eISSN
15213773
Relation.isIdenticalTo
DOI (Publisher Version)
https://doi.org/10.1002/anie.202511590
Access Rights
open access
CopyRight
This article is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
oaire:version
Version of Record
Category
学術雑誌論文 Journal Article