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タイトル: | Sodium silylsilanolate as a precursor of silylcopper species |
著者: | Yamagishi, Hiroki Hitoshio, Kenshiro Shimokawa, Jun https://orcid.org/0000-0002-4023-4640 (unconfirmed) Yorimitsu, Hideki https://orcid.org/0000-0002-0153-1888 (unconfirmed) |
著者名の別形: | 山岸, 拓幹 一入, 賢之朗 下川, 淳 依光, 英樹 |
発行日: | 21-Apr-2022 |
出版者: | Royal Society of Chemistry (RSC) |
誌名: | Chemical Science |
巻: | 13 |
号: | 15 |
開始ページ: | 4334 |
終了ページ: | 4340 |
抄録: | Silylcoppers function as convenient and effective sources of silicon functional groups. Commonly used precursors for those species have been limited to certain symmetric disilanes and silylboranes. This fact renders the development of silylcopper precursors desirable so that more diverse silyl groups could be efficiently delivered. Here we extend the utility of sodium silylsilanolates as competent precursors of silylcoppers. A silanolate unit operates as an auxiliary to transfer a variety of silyl groups to the copper centre, which was demonstrated in the copper-catalysed hydrosilylation of internal alkynes, α, β-unsaturated ketones, and allenes. Our mechanistic studies through DFT calculation suggested that a copper silylsilanolate undergoes intramolecular oxidative addition of the Si–Si bond to the copper centre to generate a silylcopper, in contrast to the typical formal σ-bond metathesis mechanism for conventional disilanes or silylboranes and copper alkoxides. Accordingly, sodium silylsilanolate has been established as an expeditious precursor of a variety of silylcopper species. |
著作権等: | © 2022 The Author(s). Published by the Royal Society of Chemistry This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. |
URI: | http://hdl.handle.net/2433/277600 |
DOI(出版社版): | 10.1039/d2sc00227b |
PubMed ID: | 35509465 |
出現コレクション: | 学術雑誌掲載論文等 |
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