Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine
Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and <i>N</i>-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nick...
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MDPI AG
2024-01-01
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| author | Weihua Mu Lin Zhu Shuya Xia Xue Tan Liangfei Duan Guanghao Meng Guo Liu |
| author_facet | Weihua Mu Lin Zhu Shuya Xia Xue Tan Liangfei Duan Guanghao Meng Guo Liu |
| author_sort | Weihua Mu |
| collection | DOAJ |
| description | Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and <i>N</i>-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the ring-opening of VCP, among which the <i>C,C_anti</i> and <i>C,C_syn</i> modes were verified to be the most accessible ones. Further explorations about four different phosphine ligand-assisted reactions based on the two most probable binding modes show that the difference in binding mode of bi- and monodentate phosphine ligands can vary the optimal reaction pathway, especially in the [3+2] cycloaddition process between the ring-opened intermediate and <i>N</i>-tosylbenzaldimine. The formation of C–C and C–N bonds between <i>N</i>-tosylbenzaldimine and the ring-opened intermediate through [3+2] cycloaddition is found to be stepwise, with the former acting as the rate-determining step (RDS) in most cases. Computed free energy barriers of RDS transition states on the optimal path <b>I</b> or <b>II</b> not only give out good predictions for reaction rates and half-lives, but also provide reasonable explanations for the major generation of <i>cis</i>-pyrrolidine. Noncovalent interaction analyses of key stationary points suggest the rate is influenced by both electronic effects and steric hindrance, while the diastereoselectivity is mainly controlled by electronic effects. |
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| language | English |
| last_indexed | 2024-03-08T11:02:15Z |
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| spelling | doaj.art-82992cfa1f1047bebd1f6df1b98ce5c42024-01-26T15:41:34ZengMDPI AGCatalysts2073-43442024-01-011418210.3390/catal14010082Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-TosylbenzaldimineWeihua Mu0Lin Zhu1Shuya Xia2Xue Tan3Liangfei Duan4Guanghao Meng5Guo Liu6Faculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaFaculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, ChinaDensity functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and <i>N</i>-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the ring-opening of VCP, among which the <i>C,C_anti</i> and <i>C,C_syn</i> modes were verified to be the most accessible ones. Further explorations about four different phosphine ligand-assisted reactions based on the two most probable binding modes show that the difference in binding mode of bi- and monodentate phosphine ligands can vary the optimal reaction pathway, especially in the [3+2] cycloaddition process between the ring-opened intermediate and <i>N</i>-tosylbenzaldimine. The formation of C–C and C–N bonds between <i>N</i>-tosylbenzaldimine and the ring-opened intermediate through [3+2] cycloaddition is found to be stepwise, with the former acting as the rate-determining step (RDS) in most cases. Computed free energy barriers of RDS transition states on the optimal path <b>I</b> or <b>II</b> not only give out good predictions for reaction rates and half-lives, but also provide reasonable explanations for the major generation of <i>cis</i>-pyrrolidine. Noncovalent interaction analyses of key stationary points suggest the rate is influenced by both electronic effects and steric hindrance, while the diastereoselectivity is mainly controlled by electronic effects.https://www.mdpi.com/2073-4344/14/1/82nickelcatalysisvinylcyclopropane (VCP)[3+2] cycloadditionmechanismDFT |
| spellingShingle | Weihua Mu Lin Zhu Shuya Xia Xue Tan Liangfei Duan Guanghao Meng Guo Liu Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine Catalysts nickel catalysis vinylcyclopropane (VCP) [3+2] cycloaddition mechanism DFT |
| title | Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine |
| title_full | Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine |
| title_fullStr | Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine |
| title_full_unstemmed | Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine |
| title_short | Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and <i>N</i>-Tosylbenzaldimine |
| title_sort | insights into the mechanism regio diastereoselectivities and ligand role of nickel initiated 3 2 cycloadditions between vinylcyclopropane and i n i tosylbenzaldimine |
| topic | nickel catalysis vinylcyclopropane (VCP) [3+2] cycloaddition mechanism DFT |
| url | https://www.mdpi.com/2073-4344/14/1/82 |
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