Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide

Ogasahara, Riku; Mae, Miyu; Matsuura, Keisuke; Yoshimura, Sota; Ishimoto, Takayoshi; Udagawa, Taro; Harada, Kazuo; Fujioka, Hiroyoshi; Kamiya, Mako; Asada, Rio; Uchiyama, Hiromasa; Tozuka, Yuichi; Akai, Shuji; Sawama, Yoshinari

doi:https://doi.org/10.1002/chem.202404204

Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide

Ogasahara, Riku; Mae, Miyu; Matsuura, Keisuke et al.

Chemistry - A European Journal, 2025, e202404204

Number of Access:1,127（2025-08-14 04:32 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/100347

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Title	Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide
Creator	CreatorName Ogasahara, Riku
	CreatorName Mae, Miyu
	CreatorName Matsuura, Keisuke
	CreatorName Yoshimura, Sota
	NRID 1000050543435 1000050543435 CreatorName Ishimoto, Takayoshi
	NRID 1000070509356 1000070509356 CreatorName Udagawa, Taro
	NRID 1000050397741 1000050397741 ORCID 0000-0002-9348-1629 0000-0002-9348-1629 researchmap permalink read0204933 read0204933 Scopus Author ID 16549528100 16549528100 CreatorName Harada, Kazuo
	CreatorName Fujioka, Hiroyoshi
	CreatorName Kamiya, Mako
	CreatorName Asada, Rio
	NRID 1000060792744 1000060792744 CreatorName Uchiyama, Hiromasa
	NRID 1000050312963 1000050312963 CreatorName Tozuka, Yuichi
	NRID 1000060192457 1000060192457 ORCID 0000-0001-9149-8745 0000-0001-9149-8745 researchmap permalink shuji_akai shuji_akai Scopus Author ID 7006001526 7006001526 CreatorName Akai, Shuji
	NRID 1000080552413 1000080552413 ORCID 0000-0002-9923-2412 0000-0002-9923-2412 researchmap permalink sawama sawama Scopus Author ID 6505798196 6505798196 CreatorName Sawama, Yoshinari
Subject	Deuterium oxide
	H/D exchange reaction
	Photocatalytic reaction
	Polyethylene glycol
Description	Ogasahara R., Mae M., Matsuura K., et al. Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide. Chemistry - A European Journal , (2025); https://doi.org/10.1002/chem.202404204.
Abstract	Deuterated molecules are of growing interest because of the specific characteristics of deuterium, such as stronger C−D bonds being stronger than C−H bonds. Polyethylene glycols (PEGs) are widely utilized in scientific fields (e. g., drug discovery and material sciences) as linkers and for the improvement of various properties (solubility in water, stability, etc.) of mother compounds. Therefore, deuterated PEGs can be used as novel tools for drug discovery. Although the H/D exchange reaction (deuteration) is a powerful and straightforward method to produce deuterated compounds, the deuteration of PEGs bearing many unactivated C(sp3)−H bonds has not been developed. Herein, we report the photocatalytic deuteration of multiple sites of PEGs using tetra-n-butylammonium decatungstate (TBADT) and D2O as an inexpensive deuterium source. This deuteration can be adapted to PEG derivatives bearing various substituents ((hetero)aryl, benzoyl, alkyl, etc.). The deuteration efficiencies of the α-oxy C(sp3)−H bonds at the terminal positions of the PEGs were strongly influenced by the substituents. These reactivities were elucidated by density functional theory calculations of the reaction barriers towards the formation of radical intermediates, induced by the excited state of TBADT and the PEG substrate. In addition, the applicability of deuterated PEGs to internal standard experiments and Raman spectroscopy was demonstrated.
Publisher	John Wiley and Sons Inc
Source Title	Chemistry - A European Journal
Page	e202404204
Date of Issued	2025-01-07
Language	English
Handle URL	https://hdl.handle.net/11094/100347
PISSN	09476539
eISSN	15213765
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/chem.202404204
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
oaire:version	Version of Record
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCTERMS.bibliographicCitation	Chemistry - A European Journal. 2025, p. e202404204
DC.title	Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide
DC.creator	Ogasahara, Riku
	Mae, Miyu
	Matsuura, Keisuke
	Yoshimura, Sota
	Ishimoto, Takayoshi
	Udagawa, Taro
	Harada, Kazuo
	Fujioka, Hiroyoshi
	Kamiya, Mako
	Asada, Rio
	Uchiyama, Hiromasa
	Tozuka, Yuichi
	Akai, Shuji
	Sawama, Yoshinari
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2025-01-07
DC.identifier	https://doi.org/10.1002/chem.202404204
DC.subject	Deuterium oxide
	H/D exchange reaction
	Photocatalytic reaction
	Polyethylene glycol
DC.description	Ogasahara R., Mae M., Matsuura K., et al. Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide. Chemistry - A European Journal , (2025); https://doi.org/10.1002/chem.202404204.
DCTERMS.abstract	Deuterated molecules are of growing interest because of the specific characteristics of deuterium, such as stronger C−D bonds being stronger than C−H bonds. Polyethylene glycols (PEGs) are widely utilized in scientific fields (e. g., drug discovery and material sciences) as linkers and for the improvement of various properties (solubility in water, stability, etc.) of mother compounds. Therefore, deuterated PEGs can be used as novel tools for drug discovery. Although the H/D exchange reaction (deuteration) is a powerful and straightforward method to produce deuterated compounds, the deuteration of PEGs bearing many unactivated C(sp3)−H bonds has not been developed. Herein, we report the photocatalytic deuteration of multiple sites of PEGs using tetra-n-butylammonium decatungstate (TBADT) and D2O as an inexpensive deuterium source. This deuteration can be adapted to PEG derivatives bearing various substituents ((hetero)aryl, benzoyl, alkyl, etc.). The deuteration efficiencies of the α-oxy C(sp3)−H bonds at the terminal positions of the PEGs were strongly influenced by the substituents. These reactivities were elucidated by density functional theory calculations of the reaction barriers towards the formation of radical intermediates, induced by the excited state of TBADT and the PEG substrate. In addition, the applicability of deuterated PEGs to internal standard experiments and Raman spectroscopy was demonstrated.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	100347
citation_title	Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide
citation_author	Ogasahara, Riku
	Mae, Miyu
	Matsuura, Keisuke
	Yoshimura, Sota
	Ishimoto, Takayoshi
	Udagawa, Taro
	Harada, Kazuo
	Fujioka, Hiroyoshi
	Kamiya, Mako
	Asada, Rio
	Uchiyama, Hiromasa
	Tozuka, Yuichi
	Akai, Shuji
	Sawama, Yoshinari
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2025-01-07
citation_journal_title	Chemistry - A European Journal
citation_firstpage	e202404204
citation_doi	https://doi.org/10.1002/chem.202404204
citation_public_url	https://hdl.handle.net/11094/100347

Photocatalytic Multiple Deuteration of Polyethylene Glycol Derivatives Using Deuterium Oxide

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