Mild Oxidative Synthesis of <i>N</i> ‐Formamides With Bio‐Based Pyruvaldehyde in Green Solvents

This work represents a catalyst‐free green protocol for the N ‐formylation of amines using pyruvaldehyde as a formyl source in ethanol under mild reaction conditions. This highly selective, catalyst‐free, and base‐free protocol enables the efficient synthesis of diverse formamides in moderate to excellent yields. It also offers a broad substrate scope, accommodating both structural and electronic variations of amines and amine‐containing heterocycles, thereby facilitating diversity generation. The avoidance of hazardous waste and the feasibility of gram‐scale synthesis represent prominent additional advantages.