电化学（中英文）2024，Vol.30Issue(5)：11-173,163.DOI:10.61558/2993-074X.3435
电化学促进的镍催化的α-氰基乙酸酯的α-芳基化反应
Nickel-Catalyzed α-Arylation of α-Cyanoacetates Enabled by Electrochemistry
摘要
Abstract
β-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 α-arylation protocol of carbonyl compounds has been developed.This protocol affords various α-aryl-α-cyanoacetates,which can be reduced to high-value-added α-aryl-β-amino acids.The cross-coupling reaction of electron-deficient aryl bromides with α-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.关键词
有机电合成/镍催化/成对电解/α-芳基化/DFT计算Key words
Organic electrosynthesis/Nickel-catalysis/Paired electrolysis/α-Arylation/DFT calculation引用本文复制引用
李子萌,李章健,Anat Milo,方萍,梅天胜..电化学促进的镍催化的α-氰基乙酸酯的α-芳基化反应[J].电化学（中英文）,2024,30(5):11-173,163.基金项目
This work was financially supported by the Na-tional Key R&D Program of China(No.2021YFA1500100),the NSF of China(Grants 21821002,21772222,and 91956112),and the S&TCSM of Shanghai(Grants 20XD1425100 and 20JC1417100). （No.2021YFA1500100）
