A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction
Conjugated diyne derivatives are important scaffolds in modern organic synthetic chemistry. Using the Glaser reaction involves the coupling of terminal alkynes which can efficiently produce conjugated diyne derivatives, while the use of a stoichiometric amount of copper salts, strong inorganic base,...
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MDPI AG
2023-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/13/5083 |
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| author | Jie Liu Yao Zhu Jun Luo Ziyi Zhu Lin Zhao Xiaoyan Zeng Dongdong Li Jun Chen Xiaobing Lan |
| author_facet | Jie Liu Yao Zhu Jun Luo Ziyi Zhu Lin Zhao Xiaoyan Zeng Dongdong Li Jun Chen Xiaobing Lan |
| author_sort | Jie Liu |
| collection | DOAJ |
| description | Conjugated diyne derivatives are important scaffolds in modern organic synthetic chemistry. Using the Glaser reaction involves the coupling of terminal alkynes which can efficiently produce conjugated diyne derivatives, while the use of a stoichiometric amount of copper salts, strong inorganic base, and excess oxidants is generally needed. Developing an environmentally friendly and effective method for the construction of symmetrical 1,3-diynes compounds by Glaser coupling is still highly desirable. In this study, we present an economical method for the production of symmetric diynes starting from various terminal acetylenes in a Glaser reaction. A simple and practical bis-N-heterocyclic carbene ligand has been introduced as efficient ligands for the Cu-catalyzed Glaser reaction. High product yields were obtained at 100 °C for a variety of substrates including aliphatic and aromatic terminal alkynes and differently substituted terminal alkynes including the highly sterically hindered substrate 2-methoxy ethynylbenzene or 2-trifluoromethyl ethynylbenzene and a series of functional groups, such as trifluoromethyl group, ester group, carboxyl group, and nitrile group. The established protocol is carried out in air under base-free condition and is operationally simple. These research work suggest that bis-N-heterocyclic carbene could also an appealing ligand for Glaser reaction and provide a reference for the preparation of symmetric 1,3-diynes in industrial filed. |
| first_indexed | 2024-03-11T01:34:21Z |
| format | Article |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T01:34:21Z |
| publishDate | 2023-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-90c6fc560e3f4cf5a53b728f20337cb92023-11-18T17:07:56ZengMDPI AGMolecules1420-30492023-06-012813508310.3390/molecules28135083A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser ReactionJie Liu0Yao Zhu1Jun Luo2Ziyi Zhu3Lin Zhao4Xiaoyan Zeng5Dongdong Li6Jun Chen7Xiaobing Lan8Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaHunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, ChinaConjugated diyne derivatives are important scaffolds in modern organic synthetic chemistry. Using the Glaser reaction involves the coupling of terminal alkynes which can efficiently produce conjugated diyne derivatives, while the use of a stoichiometric amount of copper salts, strong inorganic base, and excess oxidants is generally needed. Developing an environmentally friendly and effective method for the construction of symmetrical 1,3-diynes compounds by Glaser coupling is still highly desirable. In this study, we present an economical method for the production of symmetric diynes starting from various terminal acetylenes in a Glaser reaction. A simple and practical bis-N-heterocyclic carbene ligand has been introduced as efficient ligands for the Cu-catalyzed Glaser reaction. High product yields were obtained at 100 °C for a variety of substrates including aliphatic and aromatic terminal alkynes and differently substituted terminal alkynes including the highly sterically hindered substrate 2-methoxy ethynylbenzene or 2-trifluoromethyl ethynylbenzene and a series of functional groups, such as trifluoromethyl group, ester group, carboxyl group, and nitrile group. The established protocol is carried out in air under base-free condition and is operationally simple. These research work suggest that bis-N-heterocyclic carbene could also an appealing ligand for Glaser reaction and provide a reference for the preparation of symmetric 1,3-diynes in industrial filed.https://www.mdpi.com/1420-3049/28/13/5083conjugated diynesGlaser reactionN-heterocyclic carbenecatalysisgreen chemistry |
| spellingShingle | Jie Liu Yao Zhu Jun Luo Ziyi Zhu Lin Zhao Xiaoyan Zeng Dongdong Li Jun Chen Xiaobing Lan A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction Molecules conjugated diynes Glaser reaction N-heterocyclic carbene catalysis green chemistry |
| title | A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction |
| title_full | A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction |
| title_fullStr | A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction |
| title_full_unstemmed | A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction |
| title_short | A Simple and Practical Bis-N-Heterocyclic Carbene as an Efficient Ligand in Cu-Catalyzed Glaser Reaction |
| title_sort | simple and practical bis n heterocyclic carbene as an efficient ligand in cu catalyzed glaser reaction |
| topic | conjugated diynes Glaser reaction N-heterocyclic carbene catalysis green chemistry |
| url | https://www.mdpi.com/1420-3049/28/13/5083 |
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