Synthesis of N-formamides via oxidative carbonylation of amines with paraformaldehyde over a CoNC catalyst

Abstract

N-Formamides are important high-value chemicals with a wide array of applications. Whilst the oxidative carbonylation of amines with paraformaldehyde is a green route to synthesize N-formamides, the reaction suffers from the drawback of having to use noble metal catalysts. Herein, a non-noble metal CoNC catalyst was developed for the oxidative carbonylation of amines with paraformaldehyde. A series of N-heterocycles, aliphatic amines and anilines with different substituents were suitable for reaction over this CoNC catalyst, and moderate to good yields of the N-formylated amines were obtained. A mechanistic investigation suggests that both singlet oxygen (¹O₂) and the superoxide anion (O₂⁻) are the active oxygen species of the oxidative carbonylation reaction. Co-N_x single atom sites are the possible catalytic active sites on the CoNC catalyst.