Carbonylation of quaternary ammonium salts to tertiary amides using NaCo(CO)4 catalyst

•Carbonylation of quaternary ammonium salts under anhydrous condition were established.•Reaction activity under different conditions was investigated.•High catalytic activity and moderate to excellent yields of tertiary amides were obtained.•Intermediates and the catalytic mechanism were discussed.

We reported here the catalytic carbonylation of quaternary ammonium salts under anhydrous condition. Quaternary ammonium salts, a kind of versatile reagents that were widely used in organometallic chemistry, can be carbonylated to tertiary amides by an in situ prepared NaCo(CO)4 catalyst. It was found that the counterions (Cl−, Br−, I−, OTf−) in the quaternary ammonium salts played a significant role in the reaction and tetramethylammonium iodide could give high yield (96%) of N,N-dimethylacetamide (DMAc) with only 0.5 mol% cobalt catalyst. Under optimum conditions, several other quaternary ammonium iodides were also carbonylated to corresponding tertiary amides in moderate to excellent yields. Obviously, these results also give us a special apprehension that Me4NI and other quaternary ammonium salts could be possibly carbonylated to tertiary amides in the carbonylation reaction where they are used as promoters or solvents in most cases. Considering the high activity and moderate to excellent selectivity, this process could be a potential method for the synthesis of certain tertiary amides. Moreover, the cleaving mechanism of CN bonds and the possible catalytic intermediates were discussed in detail.

Graphical abstractCarbonylation of quaternary ammonium salts under anhydrous conditions.Figure optionsDownload full-size imageDownload high-quality image (108 K)Download as PowerPoint slide