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钯-单齿膦酰胺配体催化不对称 Markovnikov 氢氨甲酰化反应。

Asymmetric Markovnikov Hydroaminocarbonylation of Alkenes Enabled by Palladium-Monodentate Phosphoramidite Catalysis.

机构信息

Key Laboratory of Synthetic and Nature Molecule of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi'an 710127, P.R. China.

出版信息

J Am Chem Soc. 2021 Jan 13;143(1):85-91. doi: 10.1021/jacs.0c11249. Epub 2020 Dec 29.

DOI:10.1021/jacs.0c11249
PMID:33373216
Abstract

A palladium-catalyzed asymmetric Markovnikov hydroaminocarbonylation of alkenes with anilines has been developed for the atom-economical synthesis of 2-substituted propanamides bearing an α-stereocenter. A novel phosphoramidite ligand was discovered which exhibited very high reactivity and selectivity in the reaction. This asymmetric Markovnikov hydroaminocarbonylation employs readily available starting materials and tolerates a wide range of functional groups, thus providing a facile and straightforward method for the regio- and enantioselective synthesis of 2-substituted propanamides under ambient conditions. Mechanistic studies revealed that the reaction proceeds through a palladium hydride pathway.

摘要

钯催化的烯烃与苯胺的不对称 Markovnikov 氢氨甲酰化反应已经被开发出来,用于原子经济性合成具有 α-手性中心的 2-取代丙酰胺。一种新型的磷酰胺配体被发现,在反应中表现出非常高的反应活性和选择性。这种不对称 Markovnikov 氢氨甲酰化反应采用易得的起始原料,并能容忍广泛的官能团,因此在环境条件下提供了一种简便直接的方法,用于 2-取代丙酰胺的区域和对映选择性合成。机理研究表明,反应通过钯氢化物途径进行。

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