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阳离子型和均配型铜(I)-噻唑-2-亚基:高活性噻唑N-杂环卡宾σ-路易斯酸催化剂。

Cationic and Homoleptic Copper(I)-Thiazol-2-ylidenes: Highly Reactive Thiazole N-Heterocyclic Carbenes σ-Lewis Acid Catalysts.

作者信息

Wang Ruihong, Zhang Jin, Yang Hang, Zhu Yawei, Guo Yan, Han Xiaoxia, Szostak Roman, Szostak Michal

机构信息

School of Food Science and Engineering, Shaanxi University of Science and Technology, Xi'an 710021, China.

College of Chemistry and Chemical Engineering, Key Laboratory of Chemical Additives for China National Light Industry, Shaanxi University of Science and Technology, Xi'an 710021, China.

出版信息

Org Chem Front. 2025 Jul 31. doi: 10.1039/d5qo00772k.

DOI:10.1039/d5qo00772k
PMID:40843007
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12363397/
Abstract

Air- and moisture-stable cationic homoleptic Cu(I) thiazol-2-ylidene complexes are developed as highly efficient σ-Lewis acid catalysts, outperforming imidazol-2-ylidenes in the alkynylation of ketones without requiring stoichiometric Cu-acetylides. These complexes exhibit exceptional operational simplicity and robustness, enabling key C-C bond formation. Structural insights and DFT studies highlight their enhanced reactivity and stability. With their superior performance and practicality, thiazol-2-ylidenes represent a promising class of catalysts for sustainable organic synthesis.

摘要

空气和湿气稳定的阳离子型均配铜(I)噻唑-2-亚基配合物被开发为高效的σ-路易斯酸催化剂,在酮的炔基化反应中表现优于咪唑-2-亚基,且无需化学计量的炔化铜。这些配合物展现出卓越的操作简便性和稳定性,能够实现关键的碳-碳键形成。结构见解和密度泛函理论研究突出了它们增强的反应活性和稳定性。凭借其卓越的性能和实用性,噻唑-2-亚基代表了一类用于可持续有机合成的有前景的催化剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/d4f727ce1876/nihms-2100863-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/ac8744908d13/nihms-2100863-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/811a0374e38d/nihms-2100863-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/6590e3480099/nihms-2100863-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/d4f727ce1876/nihms-2100863-f0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/ac8744908d13/nihms-2100863-f0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/811a0374e38d/nihms-2100863-f0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/6590e3480099/nihms-2100863-f0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2d4b/12363397/d4f727ce1876/nihms-2100863-f0004.jpg

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本文引用的文献

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Org Lett. 2025 Apr 4;27(13):3440-3445. doi: 10.1021/acs.orglett.5c00875. Epub 2025 Mar 23.
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Gold-catalysed amine synthesis by reductive hydroamination of alkynes with nitroarenes.通过炔烃与硝基芳烃的还原氢胺化反应进行金催化的胺合成。
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Wingtip-Flexible N-Heterocyclic Carbenes: Unsymmetrical Connection between IMes and IPr.
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Angew Chem Int Ed Engl. 2024 Feb 19;63(8):e202318703. doi: 10.1002/anie.202318703. Epub 2024 Jan 16.
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Chiral Macrocyclic Catalysts for the Enantioselective Addition of Lithium Acetylides to Ketones.用于乙炔锂对酮的对映选择性加成的手性大环催化剂。
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