General, operationally simple N-dealkylation of simple and complex tertiary amines

We report a general, operationally simple N-dealkylation protocol for tertiary amines. Optimal conditions (2 equiv. PhCO₃^tBu, 1 mol% FeCl₃, 2 equiv. H₂O) enable efficient reactions at 60 °C for aliphatic amines and 80 °C for aromatic substrates. The method shows broad substrate scope, including aliphatic, benzylic, aromatic, and structurally complex amines, with good tolerance of functional groups such as halides, heterocycles, nitriles, esters, and ketones. The protocol enables direct synthesis of drug metabolites, demonstrating utility for late-stage functionalization. Control experiments support a mechanism involving hemiaminal hydrolysis. Compared to existing methods, this approach is cost-effective and broadly applicable.