电化学促进的镍催化的α-氰基乙酸酯的α-芳基化反应
收稿日期: 2023-08-27
录用日期: 2023-11-14
网络出版日期: 2023-11-21
Nickel-Catalyzed α-Arylation of α-Cyanoacetates Enabled by Electrochemistry
Received date: 2023-08-27
Accepted date: 2023-11-14
Online published: 2023-11-21
李子萌 , 李章健 , 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, 2024 , 30(5) : 2313004 . DOI: 10.61558/2993-074X.3435
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.
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