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ID 58543
フルテキストURL
著者
Murai, Masahito Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University ORCID Kaken ID publons researchmap
Yamamoto, Masaki Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University
Takai, Kazuhiko Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University ORCID Kaken ID publons researchmap
抄録
A (μ-aryloxo)rhenium complex was isolated and confirmed as a key precatalyst for rhenium-catalyzed ortho-alkenylation (C-alkenylation) of unprotected phenols with alkynes. The reaction exclusively provided ortho-alkenylphenols; the formation of para or multiply alkenylated phenols and hydrophenoxylation (O-alkenylation) products was not observed. Several mechanistic experiments excluded a classical Friedel-Crafts-type mechanism, leading to the proposed phenolic hydroxyl group assisted electrophilic alkenylation as the most plausible reaction mechanism. For this purpose, the use of rhenium, a metal between the early and late transition metals in the periodic table, was key for the activation of both the soft carbon-carbon triple bond of the alkyne and the hard oxygen atom of the phenol, at the same time. ortho-Selective alkenylation with allenes also provided the corresponding adducts with a substitution pattern different from that obtained by the addition reaction with alkynes.
キーワード
alkenylation
homogeneous catalysis
reaction mechanisms
regioselectivity
rhenium
備考
This is the peer reviewed version of the following article: [Masahito Murai et. al. Mechanistic Insights into Rhenium‐Catalyzed Regioselective C‐Alkenylation of Phenols with Internal Alkynes. Chemistry - A European Journal 25(66) 15189-15197 (2019), which has been published in final form at https://doi.org/10.1002/chem.201903910. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
発行日
2019-09-18
出版物タイトル
Chemistry - A European Journal
25巻
66号
出版者
Wiley
開始ページ
15189
終了ページ
15197
ISSN
0947-6539
NCID
AA11076269
資料タイプ
学術雑誌論文
言語
English
OAI-PMH Set
岡山大学
論文のバージョン
author
PubMed ID
DOI
Web of Science KeyUT
関連URL
isVersionOf https://doi.org/10.1002/chem.201903910
Citation
Murai M, Yamamoto M, Takai K. Mechanistic Insights into Rhenium-Catalyzed Regioselective C-Alkenylation of Phenols with Internal Alkynes. Chemistry. 2019;25(66):15189‐15197. doi:10.1002/chem.201903910
助成機関名
日本学術振興会
助成番号
18H03911