A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂

Maeji, Yuto; Kobayashi, Toshimichi; Kosugi, Kento; Saga, Yutaka; Hirahara, Masanari; Kondo, Mio; Kambe, Tetsuya; Masaoka, Shigeyuki

doi:https://doi.org/10.1002/celc.202600014

A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂

Maeji, Yuto; Kobayashi, Toshimichi; Kosugi, Kento et al.

ChemElectroChem, 2026, 13(9), e202600014

Number of Access:70（2026-08-17 04:25 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/105122

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Title	A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂
Creator	CreatorName Maeji, Yuto
	CreatorName Kobayashi, Toshimichi
	NRID 1000011002288 1000011002288 CreatorName Kosugi, Kento
	NRID 1000020785521 1000020785521 ORCID 0009-0008-3718-3222 0009-0008-3718-3222 researchmap permalink ysagagerrard ysagagerrard Scopus Author ID 36515397900 36515397900 CreatorName Saga, Yutaka
	NRID 1000090609835 1000090609835 CreatorName Hirahara, Masanari
	NRID 1000020619168 1000020619168 CreatorName Kondo, Mio
	NRID 1000000733495 1000000733495 ORCID 0000-0002-9216-2693 0000-0002-9216-2693 researchmap permalink kambe kambe Scopus Author ID 36131584400 36131584400 CreatorName Kambe, Tetsuya
	NRID 1000020404048 1000020404048 ORCID 0000-0003-2678-2269 0000-0003-2678-2269 researchmap permalink Shigeyuki_Masaoka Shigeyuki_Masaoka Scopus Author ID 7003310045 7003310045 CreatorName Masaoka, Shigeyuki
Subject	C(sp³)-H bonds
	carbon dioxide utilization
	electrosynthesis
	hydrogen atom transfer
Description	Maeji Y., Kobayashi T., Kosugi K., et al. A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂. ChemElectroChem 13, e202600014 (2026); https://doi.org/10.1002/celc.202600014.
Abstract	Direct carboxylation of C(sp³)-H bonds with carbon dioxide (CO₂) offers an attractive route to value-added carboxylic acids but remains challenging due to the inertness of both reaction partners. Here, we report a fundamentally distinct electrochemical strategy that enables carboxylation of dibenzylic C(sp³)-H bonds using hydrogen atom transfer (HAT) species reductively generated at the cathode. This represents a rare example of C(sp³)-H bond functionalization mediated by cathodically generated HAT species. In contrast to anodic HAT systems that require interelectrode diffusion of reactive intermediates, the present method allows all the elementary steps (HAT species generation, C(sp³)-H bond cleavage, and CO₂ incorporation) to occur at the same cathode. Consequently, the reaction proceeds efficiently under mild conditions (room temperature, 1 atm CO₂) without requiring an external sacrificial redox reagent, affording carboxylation products in good yields (up to 69%) within a short reaction time (2 h). Mechanistic studies support a pathway involving sequential electron transfer-chemical reaction (EC) and CO₂-coupled electron transfer processes for HAT species generation. This work establishes a mechanistically defined platform for electrochemical dibenzylic C(sp³)-H bond functionalization.
Publisher	John Wiley and Sons Inc
Source Title	ChemElectroChem
Volume (Issue)	13(9)
Page	e202600014
Date of Issued	2026-04-21
Language	English
Handle URL	https://hdl.handle.net/11094/105122
eISSN	21960216
Relation.isIdenticalTo	DOI (Publisher Version) https://doi.org/10.1002/celc.202600014
Access Rights	open access
CopyRight	This article is licensed under a Creative Commons Attribution 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
DCMI Type	Text
DCTERMS.bibliographicCitation	ChemElectroChem. 2026, 13(9), p. e202600014
DC.title	A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂
DC.creator	Maeji, Yuto
	Kobayashi, Toshimichi
	Kosugi, Kento
	Saga, Yutaka
	Hirahara, Masanari
	Kondo, Mio
	Kambe, Tetsuya
	Masaoka, Shigeyuki
DC.publisher	John Wiley and Sons Inc
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2026-04-21
DC.identifier	https://doi.org/10.1002/celc.202600014
DC.subject	C(sp³)-H bonds
	carbon dioxide utilization
	electrosynthesis
	hydrogen atom transfer
DC.description	Maeji Y., Kobayashi T., Kosugi K., et al. A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂. ChemElectroChem 13, e202600014 (2026); https://doi.org/10.1002/celc.202600014.
DCTERMS.abstract	Direct carboxylation of C(sp³)-H bonds with carbon dioxide (CO₂) offers an attractive route to value-added carboxylic acids but remains challenging due to the inertness of both reaction partners. Here, we report a fundamentally distinct electrochemical strategy that enables carboxylation of dibenzylic C(sp³)-H bonds using hydrogen atom transfer (HAT) species reductively generated at the cathode. This represents a rare example of C(sp³)-H bond functionalization mediated by cathodically generated HAT species. In contrast to anodic HAT systems that require interelectrode diffusion of reactive intermediates, the present method allows all the elementary steps (HAT species generation, C(sp³)-H bond cleavage, and CO₂ incorporation) to occur at the same cathode. Consequently, the reaction proceeds efficiently under mild conditions (room temperature, 1 atm CO₂) without requiring an external sacrificial redox reagent, affording carboxylation products in good yields (up to 69%) within a short reaction time (2 h). Mechanistic studies support a pathway involving sequential electron transfer-chemical reaction (EC) and CO₂-coupled electron transfer processes for HAT species generation. This work establishes a mechanistically defined platform for electrochemical dibenzylic C(sp³)-H bond functionalization.
DC.rights	This article is licensed under a Creative Commons Attribution 4.0 International License.
DC.format	105122
citation_title	A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂
citation_author	Maeji, Yuto
	Kobayashi, Toshimichi
	Kosugi, Kento
	Saga, Yutaka
	Hirahara, Masanari
	Kondo, Mio
	Kambe, Tetsuya
	Masaoka, Shigeyuki
citation_publisher	John Wiley and Sons Inc
citation_language	English
citation_date	2026-04-21
citation_journal_title	ChemElectroChem
citation_volume	13
citation_issue	9
citation_firstpage	e202600014
citation_doi	https://doi.org/10.1002/celc.202600014
citation_public_url	https://hdl.handle.net/11094/105122

A Cathodic Hydrogen Atom Transfer Strategy for Electrochemical Carboxylation of Dibenzylic C(sp³)-H Bonds With CO₂

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