Transition-Metal-Free Decarboxylative Amidation of Aryl <i>α</i>-Keto Acids with Diphenylphosphoryl Azide: New Avenue for the Preparation of Primary Aryl Amides

Xie, Jianwei; Shen, Li; Zhang, Jie; Gong, Shengkai

doi:10.6023/cjoc202006030

Cited by 2 publications

(1 citation statement)

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“…Amide groups widely exist in proteins, peptides, pharmaceutical intermediates, and bioactive compounds, and their order is critical for the construction of biological macromolecular frameworks . Traditional methods for the synthesis of amides include ammonolysis of active carboxylic acid derivatives, − aldehyde-alcohol condensation, and hydration of nitrile. , Although the above methods can obtain amides, the synthetic process will bring potential safety hazards, produce a large amount of chemical waste, and cause serious pollution to the environment. The direct oxidation of primary amines by a green oxidant would be an optimal alternative, , and some homogeneous or heterogeneous catalysts were developed.…”

Section: Introductionmentioning

confidence: 99%

Electrosynthesis of Amides through Cu- and Co-Incorporated Nickel Hydroxide-Catalyzed Oxidation of Primary Amines Coupled with Hydrogen Evolution

Song,

Feng,

et al. 2024

Inorg. Chem.

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The electrocatalytic oxidation of organic molecules coupled with hydrogen evolution reaction can reduce overpotential and can be connected in series with nonelectrochemical processes to achieve the preparation of more high-value compounds. Herein, Cu-and Co-incorporated nickel hydroxide (CuCo−Ni(OH) 2 ) was synthesized and applied to the anodic benzylamine oxidation reaction, which is 280 mV lower than the corresponding oxygen evolution reaction to reach the current density of 50 mA cm −2 . When the electrocatalytic oxidation of benzylamine and hydrogen evolution reaction are coupled to form an electrolytic cell, the potential to reach 10 mA cm −2 is reduced by 197 mV compared to the overall water splitting. The benzylamine is converted to benzamide with 99.3% conversion and 90.2% faraday efficiency under 1.45 V constant voltage electrolysis, and the catalytic performance remains at a high level after 4 cycles. The characterization and density functional theory calculations show that Cu and Co share the transfer charge from Ni, making it easy for CuCo−Ni(OH) 2 to deprotonate Ni−O* sites. The formed Ni−O* sites exhibit lower energy barriers in the proton transfer of benzylamine to benzonitrile and hydration intermediates, resulting in a better catalytic performance of CuCo− Ni(OH) 2 than Ni(OH) 2 in the electrocatalytic oxidation of benzylamine to benzamide.

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