Proton-Promoted Nickel-Catalyzed Asymmetric Hydrogenation of Aliphatic Ketoacids

被引：36

作者：

Deng, Chen-Qiang ^{[1
]}

Liu, Jiao ^{[1
]}

Luo, Jia-Hao ^{[1
]}

Gan, Li-Jin ^{[1
]}

Deng, Jin ^{[1
]}

Fu, Yao ^{[1
]}

机构：

[1] Univ Sci & Technol China, Dept Appl Chem, Hefei Natl Lab Phys Sci Microscale, CAS Key Lab Urban Pollutant Convers,iChEM,Anhui P, Hefei 230026, Anhui, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 15期

基金：

中国国家自然科学基金; 国家重点研发计划;

关键词：

Asymmetric Hydrogenation; Chiral Lactones; Homogeneous Catalysis; Levulinic Acid; Nickel; ENANTIOSELECTIVE HYDROGENATION; GAMMA-VALEROLACTONE; PRESSURE HYDROGENATION; ALKENE HYDROGENATION; IRON(II) COMPLEXES; HYDROXY ESTERS; LEVULINIC ACID; PINCER LIGANDS; BETA-KETO; COBALT;

D O I：

10.1002/anie.202115983

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A robust and highly active homogeneous chiral nickel-phosphine complex for the asymmetric hydrogenation of aliphatic gamma- and delta-ketoacids has been discovered. The hydrogenation could proceed smoothly in the presence of 0.0133 mol% catalyst loading (S/C=7500). The coordination chemistry and catalytic behavior of Ni(OTf)(2) with (S,S)-Ph-BPE were explored by H-1 NMR and HRMS. The mechanistic studies revealed that a proton promoted the activation of the substrate C=O bond and controlled the stereoselectivity through hydrogen bonds. A series of chiral gamma- and delta-alkyl substituted lactones were obtained in high yields with excellent enantioselectivities (up to 98 % yield and 99 % ee). In addition, this catalytic system also demonstrated that levulinic acid produced from a biomass feedstock was converted into chiral gamma-valerolactone without loss of ee value.

引用

页数：8

共 88 条

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