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

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, sh...

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Autores principales: Wang, Zi-Lu, Li, Qi, Yang, Meng-Wei, Song, Zhao-Xin, Xiao, Zhen-Yu, Ma, Wei-Wei, Zhao, Jin-Bo, Xu, Yun-He
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10439940/
https://www.ncbi.nlm.nih.gov/pubmed/37598226
http://dx.doi.org/10.1038/s41467-023-40703-1
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author Wang, Zi-Lu
Li, Qi
Yang, Meng-Wei
Song, Zhao-Xin
Xiao, Zhen-Yu
Ma, Wei-Wei
Zhao, Jin-Bo
Xu, Yun-He
author_facet Wang, Zi-Lu
Li, Qi
Yang, Meng-Wei
Song, Zhao-Xin
Xiao, Zhen-Yu
Ma, Wei-Wei
Zhao, Jin-Bo
Xu, Yun-He
author_sort Wang, Zi-Lu
collection PubMed
description 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.
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spelling pubmed-104399402023-08-21 Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes Wang, Zi-Lu Li, Qi Yang, Meng-Wei Song, Zhao-Xin Xiao, Zhen-Yu Ma, Wei-Wei Zhao, Jin-Bo Xu, Yun-He Nat Commun Article 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. Nature Publishing Group UK 2023-08-19 /pmc/articles/PMC10439940/ /pubmed/37598226 http://dx.doi.org/10.1038/s41467-023-40703-1 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Wang, Zi-Lu
Li, Qi
Yang, Meng-Wei
Song, Zhao-Xin
Xiao, Zhen-Yu
Ma, Wei-Wei
Zhao, Jin-Bo
Xu, Yun-He
Regio- and enantioselective CuH-catalyzed 1,2- and 1,4-hydrosilylation of 1,3-enynes
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
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10439940/
https://www.ncbi.nlm.nih.gov/pubmed/37598226
http://dx.doi.org/10.1038/s41467-023-40703-1
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