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Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes

Author

Listed:
  • Zi-Lu Wang

    (University of Science and Technology of China)

  • Qi Li

    (University of Science and Technology of China)

  • Meng-Wei Yang

    (University of Science and Technology of China)

  • Zhao-Xin Song

    (University of Science and Technology of China)

  • Zhen-Yu Xiao

    (University of Science and Technology of China)

  • Wei-Wei Ma

    (University of Science and Technology of China)

  • Jin-Bo Zhao

    (Changchun University of Technology)

  • Yun-He Xu

    (University of Science and Technology of China)

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.

Suggested Citation

  • Zi-Lu Wang & Qi Li & Meng-Wei Yang & Zhao-Xin Song & Zhen-Yu Xiao & Wei-Wei Ma & Jin-Bo Zhao & Yun-He Xu, 2023. "Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-40703-1
    DOI: 10.1038/s41467-023-40703-1
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    References listed on IDEAS

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    1. Meng-Yang Hu & Qiao He & Song-Jie Fan & Zi-Chen Wang & Luo-Yan Liu & Yi-Jiang Mu & Qian Peng & Shou-Fei Zhu, 2018. "Ligands with 1,10-phenanthroline scaffold for highly regioselective iron-catalyzed alkene hydrosilylation," Nature Communications, Nature, vol. 9(1), pages 1-11, December.
    2. Shaowei Chen & Xiaoqian He & Yi Jin & Yu Lan & Xiao Shen, 2022. "Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
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