Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds

Ogasahara, Riku; Mae, Miyu; Itabashi, Yuki; Ohkubo, Kei; Matsuura, Keisuke; Shimizu, Hyoga; Ban, Kazuho; Togami, Masaki; Udagawa, Taro; Fujioka, Hiroyoshi; Kamiya, Mako; Akai, Shuji; Sawama, Yoshinari

doi:https://doi.org/10.1021/jacs.5c01894

Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds

Ogasahara, Riku; Mae, Miyu; Itabashi, Yuki et al.

Journal of the American Chemical Society, 2025, 147(18), 15499-15509

アクセス数:45件（2026-06-07 12:15 集計）

固定URL: https://hdl.handle.net/11094/104548

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タイトル	Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds
著者	著者名 Ogasahara, Riku
	著者名 Mae, Miyu
	NRID 1000060971538 1000060971538 ORCID 0000-0002-5418-156X 0000-0002-5418-156X researchmap permalink yukiitabashi yukiitabashi 著者名 Itabashi, Yuki
	NRID 1000000379140 1000000379140 ORCID 0000-0001-8328-9249 0000-0001-8328-9249 researchmap permalink Kei_Ohkubo Kei_Ohkubo Scopus Author ID 7101788990 7101788990 著者名 Ohkubo, Kei
	著者名 Matsuura, Keisuke
	著者名 Shimizu, Hyoga
	著者名 Ban, Kazuho
	著者名 Togami, Masaki
	NRID 1000070509356 1000070509356 著者名 Udagawa, Taro
	NRID 1000030977236 1000030977236 著者名 Fujioka, Hiroyoshi
	NRID 1000090596462 1000090596462 著者名 Kamiya, Mako
	NRID 1000060192457 1000060192457 ORCID 0000-0001-9149-8745 0000-0001-9149-8745 researchmap permalink shuji_akai shuji_akai Scopus Author ID 7006001526 7006001526 著者名 Akai, Shuji
	NRID 1000080552413 1000080552413 ORCID 0000-0002-9923-2412 0000-0002-9923-2412 researchmap permalink sawama sawama Scopus Author ID 6505798196 6505798196 著者名 Sawama, Yoshinari
内容	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, ©American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.5c01894.
抄録	Deuterated compounds used in drug discovery and live-cell imaging have recently gained the attention of various scientific fields. Although hydrogen-deuterium (H/D) exchange reactions are straightforward deuteration methods, achieving perfect chemoselectivity is challenging. We report the highly chemoselective deuteration of α-thio C(sp3)-H bonds using a thioxanthone or anthraquinone organic photocatalyst bearing an aromatic ketone skeleton and D2O as an inexpensive deuterium source under 390 nm irradiation. Notably, incorporation of deuterium at the α-positions of the O/N atoms, benzylic positions, and aromatic rings was not observed. The present chemoselectivity was accomplished via a single electron transfer mechanism between the photocatalyst and S-containing substrates, as proven by laser-induced time-resolved transient absorption spectroscopic measurements. Furthermore, the proposed deuteration method could be applied to various S-containing substrates, including pharmaceuticals and biologically active compounds with high regioselectivities. The available deuterated compounds as novel deuterated alkylation reagents for future drug discovery and materials for Raman imaging were also demonstrated.
出版者	American Chemical Society
収録物名	Journal of the American Chemical Society
巻(号)	147(18)
ページ	15499-15509
刊行年月	2025-05-07
言語	英語
ハンドルURL	https://hdl.handle.net/11094/104548
PISSN	00027863
eISSN	15205126
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1021/jacs.5c01894
アクセス権	open access
権利情報	© 2025 American Chemical Society
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	Journal of the American Chemical Society. 2025, 147(18), p. 15499-15509
DC.title	Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds
DC.creator	Ogasahara, Riku
	Mae, Miyu
	Itabashi, Yuki
	Ohkubo, Kei
	Matsuura, Keisuke
	Shimizu, Hyoga
	Ban, Kazuho
	Togami, Masaki
	Udagawa, Taro
	Fujioka, Hiroyoshi
	Kamiya, Mako
	Akai, Shuji
	Sawama, Yoshinari
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-05-07
DC.identifier	https://doi.org/10.1021/jacs.5c01894
DC.description	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, ©American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.5c01894.
DCTERMS.abstract	Deuterated compounds used in drug discovery and live-cell imaging have recently gained the attention of various scientific fields. Although hydrogen-deuterium (H/D) exchange reactions are straightforward deuteration methods, achieving perfect chemoselectivity is challenging. We report the highly chemoselective deuteration of α-thio C(sp3)-H bonds using a thioxanthone or anthraquinone organic photocatalyst bearing an aromatic ketone skeleton and D2O as an inexpensive deuterium source under 390 nm irradiation. Notably, incorporation of deuterium at the α-positions of the O/N atoms, benzylic positions, and aromatic rings was not observed. The present chemoselectivity was accomplished via a single electron transfer mechanism between the photocatalyst and S-containing substrates, as proven by laser-induced time-resolved transient absorption spectroscopic measurements. Furthermore, the proposed deuteration method could be applied to various S-containing substrates, including pharmaceuticals and biologically active compounds with high regioselectivities. The available deuterated compounds as novel deuterated alkylation reagents for future drug discovery and materials for Raman imaging were also demonstrated.
DC.rights	© 2025 American Chemical Society
DC.format	104548
citation_title	Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds
citation_author	Ogasahara, Riku
	Mae, Miyu
	Itabashi, Yuki
	Ohkubo, Kei
	Matsuura, Keisuke
	Shimizu, Hyoga
	Ban, Kazuho
	Togami, Masaki
	Udagawa, Taro
	Fujioka, Hiroyoshi
	Kamiya, Mako
	Akai, Shuji
	Sawama, Yoshinari
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2025-05-07
citation_journal_title	Journal of the American Chemical Society
citation_volume	147
citation_issue	18
citation_firstpage	15499
citation_lastpage	15509
citation_doi	https://doi.org/10.1021/jacs.5c01894
citation_public_url	https://hdl.handle.net/11094/104548

Photocatalytic and Chemoselective H/D Exchange at α-Thio C(sp3)-H Bonds

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