A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand

Sugimoto, Hideki; Sakaida, Megumu; Shiota, Yoshihito; Miyanishi, Mayuko; Morimoto, Yuma; Yoshizawa, Kazunari; Itoh, Shinobu

doi:https://doi.org/10.1039/d3dt03429a

A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand

Sugimoto, Hideki; Sakaida, Megumu; Shiota, Yoshihito et al.

Dalton Transactions, 2024, 53(4), 1607-1615

Number of Access:502（2025-08-28 23:11 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/94620

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Title	A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand
Creator	NRID 1000000315970 1000000315970 researchmap permalink 00315970 00315970 Scopus Author ID 7201809542 7201809542 CreatorName Sugimoto, Hideki
	CreatorName Sakaida, Megumu
	NRID 1000070335991 1000070335991 CreatorName Shiota, Yoshihito
	CreatorName Miyanishi, Mayuko
	NRID 1000020719025 1000020719025 CreatorName Morimoto, Yuma
	NRID 1000030273486 1000030273486 CreatorName Yoshizawa, Kazunari
	NRID 1000030184659 1000030184659 researchmap permalink shinobuitoh shinobuitoh Scopus Author ID 7403114792 7403114792 CreatorName Itoh, Shinobu
Abstract	The catalytic activity of a rhodium(ii) dimer complex, [RhII(TMAA)]2 (TMAA = tetramethyltetraaza[14]annulene), in C-H amination reactions with organic azides is explored. Organic azides (N3-R) with an electron-withdrawing group such as a sulfonyl group (trisylazide; R = S(O)2iPr3C6H2 (Trs)) and a simple alkyl group (R = (CH2)4Ph, (CH2)2OCH2Ph, CH2Ph, or C6H4NO2) are employed in intra- and intermolecular C-H bond amination reactions. The spectroscopic analysis using ESI-mass and EPR spectroscopy techniques on the reaction intermediate generated from [RhII(TMAA)]2 and N3-R reveals that a rhodium(iii)-nitrenoid species is an active oxidant in the C-H bond amination reaction. DFT calculations suggest that the species can feature a radical localised nitrogen atom. The DFT calculation studies also indicate that the amination reaction involves hydrogen atom abstraction from the organic substrate R′-H by the NR moiety of 2N˙R and successive rebound of the generated organic radical intermediate R′˙ to [RhIII(NH-R)(TMAA)], giving [RhII(TMAA)] and R′-NH-R (amination product).
Publisher	Royal Society of Chemistry
Source Title	Dalton Transactions
Volume (Issue)	53(4)
Page	1607-1615
Date of Issued	2024-01-28
Language	English
Handle URL	https://hdl.handle.net/11094/94620
PISSN	14779226
eISSN	14779234
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1039/d3dt03429a
Access Rights	open access
CopyRight	Reproduced from Ref. Dalton Transactions, 2024, 53, 1607-1615 with permission from the Royal Society of Chemistry. https://doi.org/10.1039/d3dt03429a.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
DCMI Type	Text
DCTERMS.bibliographicCitation	Dalton Transactions. 2024, 53(4), p. 1607-1615
DC.title	A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand
DC.creator	Sugimoto, Hideki
	Sakaida, Megumu
	Shiota, Yoshihito
	Miyanishi, Mayuko
	Morimoto, Yuma
	Yoshizawa, Kazunari
	Itoh, Shinobu
DC.publisher	Royal Society of Chemistry
DC.language' scheme='DCTERMS.RFC1766	English
DC.type' scheme='DCTERMS.DCMIType	Text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-01-28
DC.identifier	https://doi.org/10.1039/d3dt03429a
DCTERMS.abstract	The catalytic activity of a rhodium(ii) dimer complex, [RhII(TMAA)]2 (TMAA = tetramethyltetraaza[14]annulene), in C-H amination reactions with organic azides is explored. Organic azides (N3-R) with an electron-withdrawing group such as a sulfonyl group (trisylazide; R = S(O)2iPr3C6H2 (Trs)) and a simple alkyl group (R = (CH2)4Ph, (CH2)2OCH2Ph, CH2Ph, or C6H4NO2) are employed in intra- and intermolecular C-H bond amination reactions. The spectroscopic analysis using ESI-mass and EPR spectroscopy techniques on the reaction intermediate generated from [RhII(TMAA)]2 and N3-R reveals that a rhodium(iii)-nitrenoid species is an active oxidant in the C-H bond amination reaction. DFT calculations suggest that the species can feature a radical localised nitrogen atom. The DFT calculation studies also indicate that the amination reaction involves hydrogen atom abstraction from the organic substrate R′-H by the NR moiety of 2N˙R and successive rebound of the generated organic radical intermediate R′˙ to [RhIII(NH-R)(TMAA)], giving [RhII(TMAA)] and R′-NH-R (amination product).
DC.rights	Reproduced from Ref. Dalton Transactions, 2024, 53, 1607-1615 with permission from the Royal Society of Chemistry. https://doi.org/10.1039/d3dt03429a.
DC.format	94620
citation_title	A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand
citation_author	Sugimoto, Hideki
	Sakaida, Megumu
	Shiota, Yoshihito
	Miyanishi, Mayuko
	Morimoto, Yuma
	Yoshizawa, Kazunari
	Itoh, Shinobu
citation_publisher	Royal Society of Chemistry
citation_language	English
citation_date	2024-01-28
citation_journal_title	Dalton Transactions
citation_volume	53
citation_issue	4
citation_firstpage	1607
citation_lastpage	1615
citation_doi	https://doi.org/10.1039/d3dt03429a
citation_public_url	https://hdl.handle.net/11094/94620

A rhodium(ii)/rhodium(iii) redox couple for C-H bond amination with alkylazides: a rhodium(iii)-nitrenoid intermediate with a tetradentate [14]-macrocyclic ligand

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