Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes
Abstract We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- and 1,2-allenylsilane products in high yields with excellent enantioselectivities (up to 99% ee). This reaction proceeds under mild condi...
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| Format: | Article |
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Nature Portfolio
2023-08-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-40703-1 |
| _version_ | 1797558560225230848 |
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| author | Zi-Lu Wang Qi Li Meng-Wei Yang Zhao-Xin Song Zhen-Yu Xiao Wei-Wei Ma Jin-Bo Zhao Yun-He Xu |
| author_facet | Zi-Lu Wang Qi Li Meng-Wei Yang Zhao-Xin Song Zhen-Yu Xiao Wei-Wei Ma Jin-Bo Zhao Yun-He Xu |
| author_sort | Zi-Lu Wang |
| collection | DOAJ |
| description | Abstract We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- and 1,2-allenylsilane products in high yields with excellent enantioselectivities (up to 99% ee). This reaction proceeds under mild conditions, shows broad substrate scope for both 1,3-enynes and trihydrosilanes, and displays excellent regioselectivities. Mechanistic studies based on deuterium-labeling reactions and density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate under both 1,2- and 1,4-hydrosilylation conditions, and it undergoes metathesis with silanes via selective four-membered or six-membered transition state, depending on the nature of the ligand. The weak interactions between the ligands and the reacting partners are found to be the key controlling factor for the observed regioselectivity switch. The origin of high enantiocontrol in the 1,4-hydrosilylation is also revealed by high level DLPNO-CCSD(T) calculations. |
| first_indexed | 2024-03-10T17:33:09Z |
| format | Article |
| id | doaj.art-fcb54b8545a2444f820168020caa4a28 |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:33:09Z |
| publishDate | 2023-08-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-fcb54b8545a2444f820168020caa4a282023-11-20T09:58:38ZengNature PortfolioNature Communications2041-17232023-08-0114111210.1038/s41467-023-40703-1Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynesZi-Lu Wang0Qi Li1Meng-Wei Yang2Zhao-Xin Song3Zhen-Yu Xiao4Wei-Wei Ma5Jin-Bo Zhao6Yun-He Xu7Department of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, University of Science and Technology of ChinaDepartment of Chemistry, University of Science and Technology of ChinaFaculty of Chemistry and Life Science, Changchun University of TechnologyDepartment of Chemistry, University of Science and Technology of ChinaAbstract We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- and 1,2-allenylsilane products in high yields with excellent enantioselectivities (up to 99% ee). This reaction proceeds under mild conditions, shows broad substrate scope for both 1,3-enynes and trihydrosilanes, and displays excellent regioselectivities. Mechanistic studies based on deuterium-labeling reactions and density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate under both 1,2- and 1,4-hydrosilylation conditions, and it undergoes metathesis with silanes via selective four-membered or six-membered transition state, depending on the nature of the ligand. The weak interactions between the ligands and the reacting partners are found to be the key controlling factor for the observed regioselectivity switch. The origin of high enantiocontrol in the 1,4-hydrosilylation is also revealed by high level DLPNO-CCSD(T) calculations.https://doi.org/10.1038/s41467-023-40703-1 |
| spellingShingle | Zi-Lu Wang Qi Li Meng-Wei Yang Zhao-Xin Song Zhen-Yu Xiao Wei-Wei Ma Jin-Bo Zhao Yun-He Xu Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes Nature Communications |
| title | Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes |
| title_full | Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes |
| title_fullStr | Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes |
| title_full_unstemmed | Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes |
| title_short | Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes |
| title_sort | regio and enantioselective cuh catalyzed 1 2 and 1 4 hydrosilylation of 1 3 enynes |
| url | https://doi.org/10.1038/s41467-023-40703-1 |
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