| アイテムタイプ |
itemtype_ver1(1) |
| 公開日 |
2025-08-28 |
| タイトル |
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タイトル |
Rh(III)-Catalyzed Oxidant-Free Dehydrogenative Mizoroki–Heck-Type Reaction: Identification of Off-Cycle Processes Potentially Limiting Catalytic Turnover |
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言語 |
en |
| 著者 |
Hirako, Naohiro
Takayanagi, Izumi
Hirayama, Daisuke
Yasui, Takeshi
Yamamoto, Yoshihiko
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| アクセス権 |
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アクセス権 |
embargoed access |
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アクセス権URI |
http://purl.org/coar/access_right/c_f1cf |
| 権利 |
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権利情報 |
This document is the Accepted Manuscript version of a Published Work that appeared in final form in [ACS Catalysis], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [https://pubs.acs.org/articlesonrequest/AOR-MAW89SREP37C8YD3VGDW].” |
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言語 |
en |
| 内容記述 |
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内容記述タイプ |
Abstract |
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内容記述 |
The Rh(III)-catalyzed dehydrogenative Mizoroki–Heck-type reaction (DMHR) has been extensively studied owing to its diverse synthetic applications. This transformation generally requires stoichiometric amounts of an external oxidant, H2 acceptor, or internal oxidizing group for efficient catalytic turnover. By contrast, the oxidant-free DMHR involving the release of H2 gas is an ideal method for minimizing waste; however, it remains underdeveloped. Here, we investigated the Rh(III)-catalyzed DMHR of 4-amino-2-quinolones under oxidant-free conditions. A combined experimental and computational study revealed that an off-cycle resting species, formed via the migratory insertion of an alkenylation product into a rhodium hydride species, was involved in the inhibition of catalytic turnover. The highly efficient oxidant-free DMHR of 4-amino-2-quinolones was achieved by excluding the coupling product from the reaction system to suppress the formation of the off-cycle resting species. Furthermore, we revisited the Rh(III)-catalyzed DMHR of aromatic substrates bearing different types of directing groups and demonstrated that substrates bearing representative directing groups such as amides, carbamates, carboxylic acids, 1-naphthol, indoles, pyridines, pyrimidines, and pyrazoles underwent alkenylation in the absence of an oxidizing agent. |
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言語 |
en |
| 出版者 |
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出版者 |
ACS Publications |
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言語 |
en |
| 言語 |
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|
言語 |
eng |
| 資源タイプ |
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資源タイプresource |
http://purl.org/coar/resource_type/c_6501 |
|
タイプ |
journal article |
| 出版タイプ |
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出版タイプ |
AM |
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出版タイプResource |
http://purl.org/coar/version/c_ab4af688f83e57aa |
| 関連情報 |
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関連タイプ |
isVersionOf |
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識別子タイプ |
DOI |
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関連識別子 |
https://doi.org/10.1021/acscatal.5c03193 |
| 収録物識別子 |
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収録物識別子タイプ |
EISSN |
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収録物識別子 |
2155-5435 |
| 書誌情報 |
en : ACS Catalysis
巻 15,
号 12,
p. 10459-10469,
発行日 2025-06-20
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| ファイル公開日 |
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日付 |
2026-06-20 |
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日付タイプ |
Available |
manuscript_0527_rev.pdf (2 MB)
