2. Academic Validation
  3. Proton-Promoted Nickel-Catalyzed Asymmetric Hydrogenation of Aliphatic Ketoacids

Proton-Promoted Nickel-Catalyzed Asymmetric Hydrogenation of Aliphatic Ketoacids

  • Angew Chem Int Ed Engl. 2022 Apr 4;61(15):e202115983. doi: 10.1002/anie.202115983.
Chen-Qiang Deng 1,  Jiao Liu 1,  Jia-Hao Luo 1,  Li-Jin Gan 1,  Jin Deng 1,  Yao Fu 1
Affiliations

Affiliation

  • 1 Hefei National Laboratory for Physical Sciences at the Microscale, iChEM, CAS Key Laboratory of Urban Pollutant Conversion, Anhui Province Key Laboratory of Biomass Clean Energy, Department of Applied Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, China.
PMID: 35099846 DOI: 10.1002/anie.202115983
Abstract

A robust and highly active homogeneous chiral nickel-phosphine complex for the asymmetric hydrogenation of aliphatic γ- and δ-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 1 H 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 γ- and δ-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 γ-valerolactone without loss of ee value.

Keywords

Asymmetric Hydrogenation; Chiral Lactones; Homogeneous Catalysis; Levulinic Acid; Nickel.

Figures
Products