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Remote Electronic Tuning of Chiral N-Heterocyclic Carbenes
https://tokushima-u.repo.nii.ac.jp/records/2011579
https://tokushima-u.repo.nii.ac.jp/records/2011579558c4044-3633-4946-848d-41319b5dda2f
| 名前 / ファイル | ライセンス | アクション |
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tcr_23_7_e202300103.pdf (2.02 MB)
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| Item type | 文献 / Documents(1) | |||||||||||||||||
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| 公開日 | 2024-02-15 | |||||||||||||||||
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| アクセス権 | open access | |||||||||||||||||
| 資源タイプ | ||||||||||||||||||
| 資源タイプ識別子 | http://purl.org/coar/resource_type/c_6501 | |||||||||||||||||
| 資源タイプ | journal article | |||||||||||||||||
| 出版社版DOI | ||||||||||||||||||
| 関連識別子 | https://doi.org/10.1002/tcr.202300103 | |||||||||||||||||
| 関連名称 | 10.1002/tcr.202300103 | |||||||||||||||||
| 出版タイプ | ||||||||||||||||||
| 出版タイプ | AM | |||||||||||||||||
| 出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||||||||||||||
| タイトル | ||||||||||||||||||
| タイトル | Remote Electronic Tuning of Chiral N-Heterocyclic Carbenes | |||||||||||||||||
| 著者 |
猪熊, 翼
× 猪熊, 翼
WEKO
666
× 山田, 健一
WEKO
842
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| 内容記述 | Our recent efforts to develop novel N-Heterocyclic carbene (NHC)-catalyzed asymmetric reactions are described. During our investigation for development of the acylation reactions via acylazoliums generated by the reactions of NHCs and α-oxidized aldehydes, we have observed significant effects of substitution at a remote site of the carbene carbon of NHCs. In addition, we also observed a significant enhancement of the enantioselectivity by the addition of carboxylate anions. From this observation, we proposed a novel working hypothesis involving a formation of a complex of the substrate and additive to reinforce the recognition of the catalyst for enhancement of the catalytic performance of the asymmetric N-heterocyclic carbene system. By applying this concept, we achieved the kinetic resolutions of both cyclic and acyclic alcohols in excellent enantioselectivities. The effects of the remote substitution were also observed in intramolecular Stetter reaction and intermolecular benzoin reaction. In these reactions, the comparison of the catalytic performance of the NHCs bearing variable remote substitutions provided insights into the reaction mechanism because the remote substitution tuned the electronic nature of NHCs without affecting the steric and electrostatic factors around the reaction site. We also developed an intramolecular benzoin condensation involving two aldehydes, which is challenging to realize. Using the substrates bearing proper protecting groups, we succeeded in the stereo divergent synthesis of a variety of inososes, which are important intermediates for the synthesis of biologically active cyclitols. | |||||||||||||||||
| キーワード | ||||||||||||||||||
| 主題 | organocatalysis | |||||||||||||||||
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| 主題 | umpolung | |||||||||||||||||
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| 主題 | N-heterocyclic carbene | |||||||||||||||||
| キーワード | ||||||||||||||||||
| 主題 | kinetic resolution | |||||||||||||||||
| キーワード | ||||||||||||||||||
| 主題 | asymmetric catalysis | |||||||||||||||||
| 書誌情報 |
en : The Chemical Record 巻 23, 号 7, p. e202300103, 発行日 2023-05-31 |
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| 収録物ID | ||||||||||||||||||
| 収録物識別子タイプ | ISSN | |||||||||||||||||
| 収録物識別子 | 15280691 | |||||||||||||||||
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| 収録物識別子タイプ | ISSN | |||||||||||||||||
| 収録物識別子 | 15278999 | |||||||||||||||||
| 出版者 | ||||||||||||||||||
| 出版者 | Wiley-VCH | |||||||||||||||||
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| 出版者 | The Chemical Society of Japan | |||||||||||||||||
| 権利情報 | ||||||||||||||||||
| 権利情報 | This is the peer reviewed version of the following article: T. Inokuma, K.-i. Yamada, The Chemical Record. 2023, 23, 7, e202300103., which has been published in final form at https://doi.org/10.1002/tcr.202300103. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited. | |||||||||||||||||
| EID | ||||||||||||||||||
| 識別子 | 397719 | |||||||||||||||||
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| 言語 | eng | |||||||||||||||||
