Pd/PVP‐Catalyzed Formylation of Amines and Nitroarenes to N‐formamides with CO2 and Dimethylamine Borane: The Influence of CO2 on the Formation of Azoxyarenes.

The reactivity of dimethylamine borane (DMAB) towards amines and nitroarenes was investigated in the presence of the CO2 and Pd/PVP (PVP = polyvinylpyrrolidone) nanocatalyst. The formation of borane formate, Me2NH.BH2(OCHO), by the insertion of CO2 into the B‐H bond was evidenced by NMR. The reaction of DMAB with CO2 also produced a second product, DMF, formed via self‐formylation. In the presence of aromatic or aliphatic amines corresponding N‐formamides were formed efficiently. Under the same conditions nitroarenes were hydrogenated to anilines or to azoxyarenes in the absence of CO2. In both reactions very high TOF values, up to 30 min‐1, were obtained. Applying a higher excess of DMAB enabled the transformation of nitroarenes to N‐formamides. The Pd/PVP catalyst was used in 7 consecutive cycles of N‐methylaniline formylation with excellent selectivity and a total TON equal to 4700.