Nickel-Catalyzed a-Arylation of a-Cyanoacetates Enabled by Electrochemistry

Zi Meng Li, Zhang Jian Li, Anat Milo, Ping Fang, Tian Sheng Mei

Research output: Contribution to journalArticlepeer-review

Abstract

b-Amino acids have a wide range of applications in the field of pharmaceuticals. Utilizing a combination strategy of nickel catalysis and paired electrolysis, a catalytic a-arylation protocol of carbonyl compounds has been developed. This protocol affords various a-aryl-a-cyanoacetates, which can be reduced to high-value-added a-aryl-b-amino acids. The cross-coupling reaction of electron-deficient aryl bromides with a-cyanoacetates achieves the expected products with good yields and functional group compatibility under mild conditions. Excessive electron-richness in initial aryl bromides facilitates the self-coupling of desired products. DFT calculations confirm that the presence of electron-rich aryl substitutions decreases the reduction potentials of the product anions, making them more susceptible to oxidation at the anode. Based on electroanalyses and mechanistic studies, it is proposed that the enolate intermediate, rather than the radical intermediate, participates in the catalytic cycle.

Original languageAmerican English
Article number2313004
JournalJournal of Electrochemistry
Volume30
Issue number5
DOIs
StatePublished - 1 Jan 2024

Keywords

  • a-Arylation
  • DFT calculation
  • Nickel-catalysis
  • Organic electrosynthesis
  • Paired electrolysis

All Science Journal Classification (ASJC) codes

  • Fuel Technology
  • Energy Engineering and Power Technology
  • Surfaces, Coatings and Films
  • Electrochemistry

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