A supported pyridylimine-cobalt catalyst for N-formylation of amines using CO₂

N-Formylation of amines with CO₂ as a cheap and non-toxic C1-feedstock and hydrosilane reducing agent is a practical and environment friendly method to synthesize formamides. This study describes an efficient and chemoselective mono-N-formylation of amines using CO₂ and phenylsilane under mild conditions using a porous metal-organic framework (MOF)-supported single-site cobalt catalyst (pyrim-UiO-Co). The pyrim-UiO-Co MOF has a UiO-topology, and its organic linkers bear a pyridylimine ligated Co catalytic moiety. A wide range of aliphatic and aromatic amines are transformed into desired N-formamides in moderate to excellent yields under 1-5 bar CO₂. Pyrim-UiO-Co is tolerant to various functional groups and could be recycled and reused at least 10 times. Mechanistic investigation using kinetic, spectroscopic and density functional theory studies suggests that the formylation of benzylamine proceeds sequentially via oxidative addition of PhSiH₃ and CO₂ insertion, followed by a turn-over limiting reaction with an amine. Our work highlights the importance of MOF-based Earth-abundant metal catalysts for the practical and eco-friendly synthesis of fine chemicals using cheap feedstocks.