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

• Published in: Nature communications Vol. 14; no. 1; p. 5048
• Main Authors: Wang, Zi-Lu, Li, Qi, Yang, Meng-Wei, Song, Zhao-Xin, Xiao, Zhen-Yu, Ma, Wei-Wei, Zhao, Jin-Bo, Xu, Yun-He
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 19.08.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 639/638/403/933; 639/638/403/934; 639/638/403/935; Copper; Density functional theory; Deuterium; Enantiomers; Humanities and Social Sciences; Hydrosilylation; Ligands; Mathematical analysis; Metathesis; multidisciplinary; Regioselectivity; Science; Science (multidisciplinary); Substrates
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-40703-1

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. Functionalization of 1,3-enyne represent a powerful method to construct allenyl- and propargylderivatives, but hydrosilylation reaction of 1,3-enynes remains underdeveloped. Here, the authors report a copper-catalyzed ligand-controlled selective 1,2- and 1,4- hydrosilylation of 1,3-enynes which proceeds enantioselectively with high yields.