Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity

Takatsuki, Masaharu; Sato, Yuta; Matsuzaki, Tsuyoshi; Sako, Makoto; Nakayama, Atsushi; Suzuki, Takeyuki; Arisawa, Mitsuhiro

doi:https://doi.org/10.1002/adsc.70276

Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity

Takatsuki, Masaharu; Sato, Yuta; Matsuzaki, Tsuyoshi et al.

Advanced Synthesis & Catalysis, 2026, 368(3), 27510

アクセス数:48件（2026-04-05 10:35 集計）

固定URL: https://hdl.handle.net/11094/103890

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タイトル	Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity
著者	著者名 Takatsuki, Masaharu
	著者名 Sato, Yuta
	著者名 Matsuzaki, Tsuyoshi
	NRID 1000020804090 1000020804090 ORCID 0000-0002-4268-7002 0000-0002-4268-7002 researchmap permalink ms39 ms39 Scopus Author ID 56014375200 56014375200 著者名 Sako, Makoto
	researchmap permalink anakaya anakaya NRID 1000060743408 1000060743408 ORCID 0000-0003-4072-3804 0000-0003-4072-3804 Scopus Author ID 56950013500 56950013500 著者名 Nakayama, Atsushi
	NRID 1000010262924 1000010262924 ORCID 0000-0002-2137-0276 0000-0002-2137-0276 researchmap permalink read0183932 read0183932 Scopus Author ID 55731626500 55731626500 著者名 Suzuki, Takeyuki
	NRID 1000040312962 1000040312962 ORCID 0000-0002-7937-670X 0000-0002-7937-670X researchmap permalink read0054866 read0054866 Scopus Author ID 7102922041 7102922041 著者名 Arisawa, Mitsuhiro
キーワード等	cycloisomerization
	hydrosilylation
	long-range isomerization
	multitask catalyst
	rhodium catalys
内容	Takatsuki Masaharu, Sato Yuta, Matsuzaki Tsuyoshi, et al. Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity. Advanced Synthesis & Catalysis 368, 27510 (2026); https://doi.org/10.1002/adsc.70276.
抄録	Multitasking catalysis offers a robust and sustainable strategy for achieving multiple transformations within a single catalytic system. Herein, we describe a rhodium-catalyzed multitasking sequence that orchestrates long-range isomerization, cycloisomerization, and hydrosilylation of 1,n-dienes in a single operation. This work represents the first demonstration of a single catalytic system capable of performing these three distinct reactions consecutively. The transformation efficiently delivers silylated 2,3-disubstituted dihydrobenzofuran derivatives, which are key structural motifs in bioactive and functional molecules. Systematic optimization revealed that the hydrosilylation step is highly sensitive to the steric and electronic properties of the silane reagent. Mechanistic investigations, including in situ ¹H NMR analyses, indicated that the hydrosilane strongly influences the equilibrium of long-range isomerization by modulating the availability of catalytically active Rh–H species. In contrast to our previously developed hydroboration system, the current hydrosilylation conditions suppress alkene migration, resulting in limited product convergence. These findings uncover how the terminal functionalization reagent governs multitasking catalysis and provide valuable insight for designing next-generation integrated catalytic systems.
出版者	Wiley
収録物名	Advanced Synthesis & Catalysis
巻(号)	368(3)
ページ	27510
刊行年月	2026-02-06
言語	英語
ハンドルURL	https://hdl.handle.net/11094/103890
PISSN	16154150
eISSN	16154169
関連情報 (isIdenticalTo)	DOI (出版社版) https://doi.org/10.1002/adsc.70276
アクセス権	open access
権利情報	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
出版タイプ	Version of Record
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	Advanced Synthesis & Catalysis. 2026, 368(3), p. 27510
DC.title	Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity
DC.creator	Takatsuki, Masaharu
	Sato, Yuta
	Matsuzaki, Tsuyoshi
	Sako, Makoto
	Nakayama, Atsushi
	Suzuki, Takeyuki
	Arisawa, Mitsuhiro
DC.publisher	Wiley
DC.language' scheme='DCTERMS.RFC1766	英語
DC.type' scheme='DCTERMS.DCMIType	text
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2026-02-06
DC.identifier	https://doi.org/10.1002/adsc.70276
DC.subject	cycloisomerization
	hydrosilylation
	long-range isomerization
	multitask catalyst
	rhodium catalys
DC.description	Takatsuki Masaharu, Sato Yuta, Matsuzaki Tsuyoshi, et al. Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity. Advanced Synthesis & Catalysis 368, 27510 (2026); https://doi.org/10.1002/adsc.70276.
DCTERMS.abstract	Multitasking catalysis offers a robust and sustainable strategy for achieving multiple transformations within a single catalytic system. Herein, we describe a rhodium-catalyzed multitasking sequence that orchestrates long-range isomerization, cycloisomerization, and hydrosilylation of 1,n-dienes in a single operation. This work represents the first demonstration of a single catalytic system capable of performing these three distinct reactions consecutively. The transformation efficiently delivers silylated 2,3-disubstituted dihydrobenzofuran derivatives, which are key structural motifs in bioactive and functional molecules. Systematic optimization revealed that the hydrosilylation step is highly sensitive to the steric and electronic properties of the silane reagent. Mechanistic investigations, including in situ ¹H NMR analyses, indicated that the hydrosilane strongly influences the equilibrium of long-range isomerization by modulating the availability of catalytically active Rh–H species. In contrast to our previously developed hydroboration system, the current hydrosilylation conditions suppress alkene migration, resulting in limited product convergence. These findings uncover how the terminal functionalization reagent governs multitasking catalysis and provide valuable insight for designing next-generation integrated catalytic systems.
DC.rights	This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
DC.format	103890
citation_title	Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity
citation_author	Takatsuki, Masaharu
	Sato, Yuta
	Matsuzaki, Tsuyoshi
	Sako, Makoto
	Nakayama, Atsushi
	Suzuki, Takeyuki
	Arisawa, Mitsuhiro
citation_publisher	Wiley
citation_language	英語
citation_date	2026-02-06
citation_journal_title	Advanced Synthesis & Catalysis
citation_volume	368
citation_issue	3
citation_firstpage	27510
citation_doi	https://doi.org/10.1002/adsc.70276
citation_public_url	https://hdl.handle.net/11094/103890

Rhodium Multitasking Catalysis Integrating Long‐Range Isomerization, Cycloisomerization, and Hydrosilylation of 1,n‐Dienes to Give 2,3‐Disubstituted Dihydrobenzofurans: Mechanistic Insight Into Functionalization‐Controlled Reactivity

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