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Cobalt-Catalyzed Synthesis of Unsymmetrically N,N-Disubstituted Formamides via Reductive Coupling of Primary Amines and Aldehydes with CO₂ and H₂
- Ke, Zhengang, Yang, Zhenzhen, Liu, Zhenghui, Yu, Bo, Zhao, Yanfei, Guo, Shien, Wu, Yunyan, Liu, Zhimin
- Organic letters 2018 v.20 no.21 pp. 6622-6626
- aldehydes, carbon dioxide, chemical structure, formic acid, hydrogen, hydrogenation, imines, potassium carbonate, primary amines
- Herein, a novel route to synthesize unsymmetrically N,N-disubstituted formamides is reported, which is achieved via reductive coupling of primary amine and aldehyde with CO₂/H₂ over a cobalt-based catalytic system composed of CoF₂, P(CH₂CH₂PPh₂)₃ and K₂CO₃. The mechanism investigation indicates that a secondary amine is formed via hydrogenation of the imine originated from aldehyde and primary amine, which further reacts with HCOOH generated from CO₂ hydrogenation, resulting in the formation of NNFA finally.