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Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N‑Dimethylformamide
http://hdl.handle.net/2237/27077
http://hdl.handle.net/2237/27077939c00bf-c5e7-4e80-8174-bd4ccc8ff89d
| 名前 / ファイル | ライセンス | アクション |
|---|---|---|
JOC_MS_rev.pdf ファイル公開日:2018/08/04 (895.1 kB)
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| アイテムタイプ | 学術雑誌論文 / Journal Article(1) | |||||
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| 公開日 | 2017-11-08 | |||||
| タイトル | ||||||
| タイトル | Combined Experimental and Computational Study on Ruthenium(II)-Catalyzed Reactions of Diynes with Aldehydes and N,N‑Dimethylformamide | |||||
| 言語 | en | |||||
| 著者 |
Yoshihiko, Yamamoto
× Yoshihiko, Yamamoto× Yuta, Okude× Shota, Mori× Masatoshi, Shibuya |
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| アクセス権 | ||||||
| アクセス権 | open access | |||||
| アクセス権URI | http://purl.org/coar/access_right/c_abf2 | |||||
| 権利 | ||||||
| 権利情報 | “This document is the Accepted Manuscript version of a Published Work that appeared in final form in [Journal of Organic Chemistry], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [ http://pubs.acs.org/articlesonrequest/AOR-gsXP3SHHURzcsmdS3cwp].” | |||||
| 言語 | en | |||||
| 抄録 | ||||||
| 内容記述タイプ | Abstract | |||||
| 内容記述 | Cycloaddition reactions of 1,6-diynes bearing methyl terminal groups with p-anisaldehyde were conducted using a cationic ruthenium catalyst with a η^5 -pentamethylcyclopentadienyl ligand in THF at room temperature to afford dienyl ketones via ring opening of the initially formed fused pyrans. (Z)-Stereoisomers of dienyl ketones were selectively obtained using the ruthenium catalyst, whereas previously reported rhodium catalysts produced (E)-isomers. These (E)- and (Z)-selectivities are kinetically controlled as the control experiments showed that the E/Z-isomerization of (E)-dienylketone occurs at 70 °C for 10 h to afford an E/Z-ratio of almost 1:1. The origin of this characteristic stereoselectivity for the ruthenium catalyst was attributed to the direct ring opening of the CpRu^+ -coordinated pyran complex intermediates on the basis of theoretical calculations [PCM (THF) M06L/SDD-6-311++G(d,p)//B3LYP/LanL2DZ-6-31G(d)] and control experiments. The (Z)-selectivity increased when the bulkiness of the diyne terminal substituents increased. Notably, the reaction of 1,6-diynes bearing tert-butyl terminal groups with various α,β-unsaturated aldehydes exclusively afforded (Z)-dienyl ketones even at 70 °C when a cationic ruthenium complex with a smaller η^5 -cyclopentadienyl (Cp) ligand was used as the catalyst. The same Cp complex was found to be also efficient for the hydrocarbamoylative cyclization of sterically demanding 1,6-diynes bearing tertiary or quaternary carbon tethers with N,N-dimethylformamide. | |||||
| 言語 | en | |||||
| 出版者 | ||||||
| 出版者 | ACS Publications | |||||
| 言語 | en | |||||
| 言語 | ||||||
| 言語 | eng | |||||
| 資源タイプ | ||||||
| 資源タイプresource | http://purl.org/coar/resource_type/c_6501 | |||||
| タイプ | journal article | |||||
| 出版タイプ | ||||||
| 出版タイプ | AM | |||||
| 出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
| DOI | ||||||
| 関連タイプ | isVersionOf | |||||
| 識別子タイプ | DOI | |||||
| 関連識別子 | https://doi.org/10.1021/acs.joc.7b01229 | |||||
| ISSN | ||||||
| 収録物識別子タイプ | PISSN | |||||
| 収録物識別子 | 0022-3263 | |||||
| 書誌情報 |
en : Journal of Organic Chemistry 巻 82, 号 15, p. 7964-7973, 発行日 2017-08-04 |
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| 著者版フラグ | ||||||
| 値 | author | |||||
| URI | ||||||
| 識別子 | http://doi.org/10.1021/acs.joc.7b01229 | |||||
| 識別子タイプ | DOI | |||||
| URI | ||||||
| 識別子 | http://hdl.handle.net/2237/27077 | |||||
| 識別子タイプ | HDL | |||||
