Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes DOI Creative Commons
Zi‐Lu Wang, Qi Li,

Meng‐Wei Yang

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Feb. 1, 2023

Abstract We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- 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 trihydrosilanes, displays regioselectivities. Mechanistic studies based on deuterium-labeling reactions density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate it undergoes metathesis silanes via four-membered or six-membered transition state, depending nature ligand. The weak interactions between ligands reacting partners are found be key controlling factor observed regioselectivity switch.

Language: Английский

Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes DOI Creative Commons
Zi‐Lu Wang, Qi Li,

Meng‐Wei Yang

et al.

Research Square (Research Square), Journal Year: 2023, Volume and Issue: unknown

Published: Feb. 1, 2023

Abstract We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- 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 trihydrosilanes, displays regioselectivities. Mechanistic studies based on deuterium-labeling reactions density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate it undergoes metathesis silanes via four-membered or six-membered transition state, depending nature ligand. The weak interactions between ligands reacting partners are found be key controlling factor observed regioselectivity switch.

Language: Английский

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