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钯催化的亚甲基环丙烷对映选择性和区域选择性开环膦氢化反应。

Palladium-Catalyzed Enantio- and Regioselective Ring-Opening Hydrophosphinylation of Methylenecyclopropanes.

机构信息

Department of Chemistry, Hong Kong Baptist University Kowloon, Hong Kong, China.

Department of Chemistry, Southern University of Science and Technology Shenzhen, Guangdong, 518055, China.

出版信息

Angew Chem Int Ed Engl. 2023 Jun 26;62(26):e202303727. doi: 10.1002/anie.202303727. Epub 2023 May 16.

Abstract

Transition metal-catalyzed hydrofunctionalization of methylenecyclopropanes (MCPs) has presented a considerable challenge due to the difficult manipulation of regioselectivity and complicated reaction patterns. Herein, we report a straightforward Pd-catalyzed ring-opening hydrophosphinylation reaction of MCPs via highly selective C-C bond cleavage. This method allows for rapid and efficient access to a wide range of chiral allylic phosphine oxides in good yields and high enantioselectivities. Additionally, density functional theory (DFT) calculations were performed to elucidate the reaction mechanism and the origin of enantioselectivity.

摘要

由于难以控制区域选择性和复杂的反应模式,过渡金属催化的亚甲基环丙烷(MCPs)的氢官能化一直是一个巨大的挑战。在此,我们报告了一种通过高度选择性的 C-C 键断裂实现 MCPs 的钯催化开环氢膦化反应的简便方法。该方法可快速有效地获得广泛的手性烯丙基氧化膦,产率高,对映选择性好。此外,还进行了密度泛函理论(DFT)计算,以阐明反应机理和对映选择性的起源。

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