Catalytic and Mechanistic Approach to the Metal-Free N-Alkylation of 2-Aminopyridines with Diketones.

N-alkylation of amines is an important catalytic reaction in synthetic chemistry. Herein, we report a simple strategy for the N-alkylation of 2-aminopyridines with 1,2-diketones using BF3·OEt2 as a catalyst. The reaction proceeds under aerobic conditions, leading to the formation of a diverse range of substituted secondary amines in good to excellent yields. A close inspection of the mechanistic pathway using various spectroscopic techniques and the computational study revealed that the reaction proceeds through the formation of an iminium-keto intermediate with the liberation of CO2.