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

Zi-Lu Wang, Qi Li, Meng-Wei Yang, Zhao-Xin Song, Zhen-Yu Xiao, Wei-Wei Ma, Jin-Bo Zhao () and Yun-He Xu ()
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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

Nature Communications, 2023, vol. 14, issue 1, 1-12

Abstract: 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.

Date: 2023
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DOI: 10.1038/s41467-023-40703-1

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