Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines

Yasui, Kosuke; Miyaoka, Masayuki; Tomishima, Yuichiro; Hirano, Koji

doi:https://doi.org/10.1093/bulcsj/uoaf043

Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines

Yasui, Kosuke; Miyaoka, Masayuki; Tomishima, Yuichiro et al.

Bulletin of the Chemical Society of Japan, 2025, 98(6), uoaf043

アクセス数:65件（2026-02-15 23:45 集計）

固定URL: https://hdl.handle.net/11094/103358

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タイトル	Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines
著者	NRID 1000010877640 1000010877640 ORCID 0000-0002-3906-8307 0000-0002-3906-8307 researchmap permalink k_yasui k_yasui Scopus Author ID 58881383300 58881383300 著者名 Yasui, Kosuke
	著者名 Miyaoka, Masayuki
	著者名 Tomishima, Yuichiro
	NRID 1000070532696 1000070532696 ORCID 0000-0001-9752-1985 0000-0001-9752-1985 researchmap permalink koj koj Scopus Author ID 7402407063 7402407063 著者名 Hirano, Koji
キーワード等	mesolytic cleavage
	sulfoximines
	α-fluorovinyl radical
内容	This is a pre-copyedited, author-produced version of an article accepted for publication in Bulletin of the Chemical Society of Japan following peer review. The version of record Yasui K., Miyaoka M., Tomishima Y., et al. Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines. Bulletin of the Chemical Society of Japan 98, uoaf043 (2025) is available online at: https://doi.org/10.1093/bulcsj/uoaf043.
抄録	An unusual configurational stability of the α-fluorovinyl radical holds significant potential to synthesize valuable monofluoroalkenes, bioisosteres of amides, in a stereoselective fashion. However, the lack of a suitable precursor for this radical, generated in a stereoselective manner, has hindered its application to the stereoselective synthesis of monofluoroalkenes. Herein, we report the stereoselective generation of the α-fluorovinyl radical, which reacts with disulfide to form α-fluorovinyl sulfides. This method hinges on two key reactions: stereoselective condensation of N-pivaloyl fluoromethyl sulfoximine with an aldehyde to form α-fluorovinyl sulfoximine, and a substitution radical-nucleophilic unimolecular (Sʀɴ1)-type reaction involving the nontrivial mesolytic cleavage of the C(sp²)-S bond of the resulting α-fluorovinyl sulfoximines. The generation of the α-fluorovinyl radical was supported by a density functional theory calculation, the Arrhenius equation, and the stereospecificity of the substitution with retention of its original stereochemistry.
出版者	Oxford University Press
収録物名	Bulletin of the Chemical Society of Japan
巻(号)	98(6)
ページ	uoaf043
刊行年月	2025-06-01
言語	英語
ハンドルURL	https://hdl.handle.net/11094/103358
PISSN	00092673
eISSN	13480634
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1093/bulcsj/uoaf043
アクセス権	embargoed access
権利情報	The full-text file will be made open to the public on 1 June 2026 in accordance with the publisher's policy.
出版タイプ	Accepted Manuscript
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	Bulletin of the Chemical Society of Japan. 2025, 98(6), p. uoaf043
DC.title	Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines
DC.creator	Yasui, Kosuke
	Miyaoka, Masayuki
	Tomishima, Yuichiro
	Hirano, Koji
DC.publisher	Oxford University Press
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-06-01
DC.identifier	https://doi.org/10.1093/bulcsj/uoaf043
DC.subject	mesolytic cleavage
	sulfoximines
	α-fluorovinyl radical
DC.description	This is a pre-copyedited, author-produced version of an article accepted for publication in Bulletin of the Chemical Society of Japan following peer review. The version of record Yasui K., Miyaoka M., Tomishima Y., et al. Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines. Bulletin of the Chemical Society of Japan 98, uoaf043 (2025) is available online at: https://doi.org/10.1093/bulcsj/uoaf043.
DCTERMS.abstract	An unusual configurational stability of the α-fluorovinyl radical holds significant potential to synthesize valuable monofluoroalkenes, bioisosteres of amides, in a stereoselective fashion. However, the lack of a suitable precursor for this radical, generated in a stereoselective manner, has hindered its application to the stereoselective synthesis of monofluoroalkenes. Herein, we report the stereoselective generation of the α-fluorovinyl radical, which reacts with disulfide to form α-fluorovinyl sulfides. This method hinges on two key reactions: stereoselective condensation of N-pivaloyl fluoromethyl sulfoximine with an aldehyde to form α-fluorovinyl sulfoximine, and a substitution radical-nucleophilic unimolecular (Sʀɴ1)-type reaction involving the nontrivial mesolytic cleavage of the C(sp²)-S bond of the resulting α-fluorovinyl sulfoximines. The generation of the α-fluorovinyl radical was supported by a density functional theory calculation, the Arrhenius equation, and the stereospecificity of the substitution with retention of its original stereochemistry.
DC.rights	The full-text file will be made open to the public on 1 June 2026 in accordance with the publisher's policy.
DC.format	103358
citation_title	Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines
citation_author	Yasui, Kosuke
	Miyaoka, Masayuki
	Tomishima, Yuichiro
	Hirano, Koji
citation_publisher	Oxford University Press
citation_language	英語
citation_date	2025-06-01
citation_journal_title	Bulletin of the Chemical Society of Japan
citation_volume	98
citation_issue	6
citation_firstpage	uoaf043
citation_doi	https://doi.org/10.1093/bulcsj/uoaf043
citation_public_url	https://hdl.handle.net/11094/103358

Stereoselective generation and use of α-fluorovinyl radicals via mesolytic cleavage of the C(sp²)-S bond of α-fluorovinyl sulfoximines

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