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镍催化的β-(酰氨基)丙烯酯的对映选择性氢化:手性β-氨基酸衍生物的合成。

Nickel-Catalyzed Enantioselective Hydrogenation of β-(Acylamino)acrylates: Synthesis of Chiral β-Amino Acid Derivatives.

机构信息

Key Laboratory of Biomedical Polymers, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University , Wuhan, Hubei 430072, China.

Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University , Wuhan, Hubei 430072, China.

出版信息

Org Lett. 2017 Oct 6;19(19):5130-5133. doi: 10.1021/acs.orglett.7b02417. Epub 2017 Sep 11.

DOI:10.1021/acs.orglett.7b02417
PMID:28892636
Abstract

The nickel-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates has been developed, affording chiral β-amino acid derivatives with excellent yields (95-99% yield) and enantioselectivities (97-99% ee). With the Ni-Binapine system, high enantioselectivities (98-99% ee) have also been obtained in the hydrogenation of Z/E isomeric mixtures of β-alkyl and β-aryl β-(acylamino)acrylates. The synthesis of chiral β-amino acid derivatives on a gram scale has also been achieved with 0.2 mol % catalyst loading.

摘要

已开发出镍催化的β-(酰氨基)丙烯酸盐的不对称氢化反应,以优异的收率(95-99%收率)和对映选择性(97-99%ee)得到手性β-氨基酸衍生物。使用 Ni-Binapine 体系,在氢化 Z/E 异构体混合物的β-烷基和β-芳基β-(酰氨基)丙烯酸盐时也获得了高对映选择性(98-99%ee)。在手性β-氨基酸衍生物的克级规模合成中,催化剂用量为 0.2mol%时也能实现。

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