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A chitosan‐derived metal‐free N‐doped carbon catalyst was synthesized and investigated for selective reductive formylation of quinoline to N‐formyl‐tetrahydroquinoline and nitroarenes to N‐formyl anilides via aqueous formic acid (FA)‐mediated catalytic transformation. FA dissociated on the catalyst surface and acted as a hydrogenating and formylating source for selective N‐formylation of N‐heteroarenes. The carbonized catalyst prepared at 700 °C offered the best activity. A 92 % yield of N‐formyl‐tetrahydroquinoline after 14 h and >99 % yield for N‐formyl anilide after 12 h at 160 °C were obtained. The excellent catalytic activity was correlated with the type of “N” species and the basicity of the catalyst. Density functional theory calculations revealed that a water‐assisted FA decomposition pathway (deprotonation and dehydroxylation) generated the surface adsorbed −H and −HCOO species, required for the formation of N‐formylated products. In addition, the selective formation of N‐formyl‐tetrahydroquinoline and N‐formyl anilides was explained by a comprehensive reaction energetics analysis.

The selective hydrogenation of unsaturated carbonyl compounds requires a catalyst with a suitable combination of support and active sites to activate a specific functional group. In this work, ZnO and...

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The Cover Feature shows a metal‐free, N‐doped carbon‐mediated sustainable catalytic route for selective reductive formylation of quinoline to N‐formyl‐tetrahydroquinoline and nitroarenes to N‐formyl anilides via aqueous formic acid mediated catalytic transformation. The boat (built with chitosan derived from crabs) represents the chitosan‐derived N‐doped carbon catalyst sailing in the water containing formic acid. More information can be found in the Research Article by A. Chauhan et al.