Cobalt-Catalyzed Synthesis of Unsymmetrically N, N-Disubstituted Formamides via Reductive Coupling of Primary Amines and Aldehydes with CO and H.

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 CO/H over a cobalt-based catalytic system composed of CoF, P(CHCHPPh) and KCO. 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 CO hydrogenation, resulting in the formation of NNFA finally.