The efficiency of N,N‐dimethylformamide (DMF) in the N‐heterocyclic carbene‐catalyzed Mannich reaction for the synthesis of β‐amino ketones has been demonstrated. This strategy involves oxidative coupling of aryl methyl ketones and 2‐aminopyridines in the presence of DMF. The reaction does not require pre‐functionalization of the substrates, thus making it a practically applicable approach for the generation of β‐amino ketones. The reaction requires the use of tin(II) chloride dihydrate (SnCl2⋅2 H2O) as Lewis acid in the presence of tert‐butyl hydroperoxide (TBHP) as the oxidant. The reaction was tolerant to several aryl methyl ketones, including 2‐acetylnaphthalene and acetylthiophene. Various substituted 2‐aminopyridines react with acetophenone to give the desired β‐amino ketones in good yields.