Based on our continuous interest in organofluorine methodologies and owing to the excellent nucleophilicity of the nitrogen atom in N-heterocycles, we hypothesized that difluoromethyl species could selectively difluoromethylate the nitrogen atom in the heterocycle (Figure ). Once the activated heteroarenium salt is generated, it increases the acidity of the hydrogen atom in the external N-H bond of N-heterocycles. Next, deprotonation and π electron transfer from the external nitrogen atom of amine to the nitrogen atom of the heteroarene enables the unprecedented N-difluoromethylative dearomatized product (Figure ). According to this concept, we sought to investigate the reactivity of bromo(difluoro)acetic acid (commercially available, a benchtop stable and inexpensive solid) and introduce a new platform for the preparation of previously unexplored Ndifluoromethylated compounds with the concurrent formation of a new imine or ketone moiety (Figure ), which is unusual compared to classical and/or already reported methods. Overall, this unique methodology was transition metal-free, safe, practical, scalable (>50 grams), tolerant to numerous reactive functional groups with excellent chemoselectivity, adaptable for important N-heterocyclic systems, and could be used for the late-stage diversification of 18 commercial drug molecules. Exceptionally, the synthesized products in this work encompass a comprehensive package of medicinally important functionalities (quinoline, -NCF2H, and imine/keto), making it immediately applicable in the preparation of chemical libraries and innovative pharmaceuticals.