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

Kato, Shunsuke; Nishiwaki, Haruka; Endo, Keiji; Hayashi, Takashi

doi:https://doi.org/10.1002/anie.202511590

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

アクセス数:206件（2026-02-15 23:06 集計）

固定URL: https://hdl.handle.net/11094/102955

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タイトル	Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases
著者	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 著者名 Kato, Shunsuke
	著者名 Nishiwaki, Haruka
	著者名 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 著者名 Hayashi, Takashi
キーワード等	Aldoxime dehydratase
	Biocatalysis
	Hemoproteins
	Iminyl radicals
	Oximes
内容	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.
抄録	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.
出版者	John Wiley and Sons Inc
収録物名	Angewandte Chemie - International Edition
ページ	e202511590
刊行年月	2025-08-21
言語	英語
ハンドルURL	https://hdl.handle.net/11094/102955
PISSN	14337851
eISSN	15213773
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/anie.202511590
アクセス権	open access
権利情報	This article is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
出版タイプ	Version of Record
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCMI資源タイプ	text
DCTERMS.bibliographicCitation	Angewandte Chemie - International Edition. 2025, p. e202511590
DC.title	Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases
DC.creator	Kato, Shunsuke
	Nishiwaki, Haruka
	Endo, Keiji
	Hayashi, Takashi
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-08-21
DC.identifier	https://doi.org/10.1002/anie.202511590
DC.subject	Aldoxime dehydratase
	Biocatalysis
	Hemoproteins
	Iminyl radicals
	Oximes
DC.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.
DCTERMS.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.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
DC.format	102955
citation_title	Radical Ring-Opening Reaction of Non-Activated Oximes Catalyzed by Aldoxime Dehydratases
citation_author	Kato, Shunsuke
	Nishiwaki, Haruka
	Endo, Keiji
	Hayashi, Takashi
citation_publisher	John Wiley and Sons Inc
citation_language	英語
citation_date	2025-08-21
citation_journal_title	Angewandte Chemie - International Edition
citation_firstpage	e202511590
citation_doi	https://doi.org/10.1002/anie.202511590
citation_public_url	https://hdl.handle.net/11094/102955

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

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