LAUSR

Cu/TEMPO as catalytic system is known for the selective transformation of alcohol to aldehyde as well as the simultaneous coupling of alcohol and amines to imines under oxidative conditions. Herein we demonstrate for the first time that such a Cu/TEMPO catalyst system is able to catalyse the N -formylation of a variety of amines by initial oxidative activation of methanol as the carbonyl source via formaldehyde and formation of N,O -halfacetals and oxidation of the latter ones at very mild conditions. A vast range of amines, from aromatic and aliphatic primary and secondary, as well as linear and cyclic amines have been formylated under these conditions with good to excellent yields. Additionally, we demonstrate here that paraformaldehyde can be used instead of methanol for the N -formylation.