Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study
Density functional theory (DFT) was used to investigate the three-component coupling reactions of aldehydes, alkynes, and amines (A3 coupling) using N-heterocyclic carbene silver as the catalyst. This study reveals that the addition reaction between the catalyst N-heterocyclic carbene silver and phe...
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MDPI AG
2023-03-01
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| Online Access: | https://www.mdpi.com/2073-4344/13/4/646 |
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| author | Chenggen Zhang Shuyuan Yu Fei Wang Jian Cao Xinru Liang Fuping Wang Huimin Zheng Yaning Zhang Mengyao Yang Boyu Zhao |
| author_facet | Chenggen Zhang Shuyuan Yu Fei Wang Jian Cao Xinru Liang Fuping Wang Huimin Zheng Yaning Zhang Mengyao Yang Boyu Zhao |
| author_sort | Chenggen Zhang |
| collection | DOAJ |
| description | Density functional theory (DFT) was used to investigate the three-component coupling reactions of aldehydes, alkynes, and amines (A3 coupling) using N-heterocyclic carbene silver as the catalyst. This study reveals that the addition reaction between the catalyst N-heterocyclic carbene silver and phenylacetylene (PAE) forms Ag_PAE. Subsequently, one hydrogen atom of the Ag_PAE migrates to the nitrogen atom of the Amine. Thereafter, the amine aldehyde condensation reaction generates a molecule of water and an imine ion with (Path one) or without (Path two) another amine catalyst. Path one has a lower reaction barrier than Path two. Subsequently, the imine ion reacts with silver phenylacetylide to generate the A3 coupling reaction product propargylamine (PPA). Furthermore, the triple bond and −N<sub>3</sub> group in PPA undergo a cycloaddition reaction and generate the final product (PR). The entire reaction is strongly exothermic, and, therefore, the reaction is easy to conduct. Moreover, conceptual density functional theory calculations confirm the reaction mechanism. Investigating the mechanism of these reactions will be helpful for understanding and developing new synthesis strategies for similar functional compounds. |
| first_indexed | 2024-03-11T05:09:05Z |
| format | Article |
| id | doaj.art-6a08121525294f9fb518501b6189073c |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-11T05:09:05Z |
| publishDate | 2023-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-6a08121525294f9fb518501b6189073c2023-11-17T18:40:35ZengMDPI AGCatalysts2073-43442023-03-0113464610.3390/catal13040646Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT StudyChenggen Zhang0Shuyuan Yu1Fei Wang2Jian Cao3Xinru Liang4Fuping Wang5Huimin Zheng6Yaning Zhang7Mengyao Yang8Boyu Zhao9College of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaCollege of Chemistry and Material Science, Langfang Normal University, Langfang 065000, ChinaDensity functional theory (DFT) was used to investigate the three-component coupling reactions of aldehydes, alkynes, and amines (A3 coupling) using N-heterocyclic carbene silver as the catalyst. This study reveals that the addition reaction between the catalyst N-heterocyclic carbene silver and phenylacetylene (PAE) forms Ag_PAE. Subsequently, one hydrogen atom of the Ag_PAE migrates to the nitrogen atom of the Amine. Thereafter, the amine aldehyde condensation reaction generates a molecule of water and an imine ion with (Path one) or without (Path two) another amine catalyst. Path one has a lower reaction barrier than Path two. Subsequently, the imine ion reacts with silver phenylacetylide to generate the A3 coupling reaction product propargylamine (PPA). Furthermore, the triple bond and −N<sub>3</sub> group in PPA undergo a cycloaddition reaction and generate the final product (PR). The entire reaction is strongly exothermic, and, therefore, the reaction is easy to conduct. Moreover, conceptual density functional theory calculations confirm the reaction mechanism. Investigating the mechanism of these reactions will be helpful for understanding and developing new synthesis strategies for similar functional compounds.https://www.mdpi.com/2073-4344/13/4/646A3 coupling reactionN-heterocyclic carbene silverreaction mechanismDFT calculations |
| spellingShingle | Chenggen Zhang Shuyuan Yu Fei Wang Jian Cao Xinru Liang Fuping Wang Huimin Zheng Yaning Zhang Mengyao Yang Boyu Zhao Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study Catalysts A3 coupling reaction N-heterocyclic carbene silver reaction mechanism DFT calculations |
| title | Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study |
| title_full | Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study |
| title_fullStr | Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study |
| title_full_unstemmed | Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study |
| title_short | Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study |
| title_sort | insights into the three component coupling reactions of aldehydes alkynes and amines catalyzed by n heterocyclic carbene silver a dft study |
| topic | A3 coupling reaction N-heterocyclic carbene silver reaction mechanism DFT calculations |
| url | https://www.mdpi.com/2073-4344/13/4/646 |
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