2-Aminopyridine is a versatile scaffold in medicinal chemistry, forming the core of numerous drugs with diverse biological activities, including anticancer, antioxidant, antibacterial, antifungal, antiviral, anti-inflammatory, antimalarial, antidiabetic, antileishmanial, and antitrypanosomal properties. Its ortho-amino group and pyridine nitrogen enable the construction of diverse polyheterocycles. However, conventional approaches to 2-aminopyridines often rely on prefunctionalized substrates, harsh conditions, or transition-metal catalysis, limiting structural diversity and synthetic accessibility. To address these challenges, we developed a metal-free, one-pot strategy to access 4-aryl-2-aminopyridine N-oxides as versatile precursors to 2-aminopyridines. This method employs vinylogous enamino nitriles and NH₂OH·HCl, combining hydroxylamine-mediated transamidation with cyclization of acid-activated enamines in a rapid, operationally simple, and high-yielding process. Using this approach, eight functionalized aryl derivatives were synthesized, and additional substituent introduction is ongoing to further expand the scope. This strategy offers broad functional group tolerance and strong potential for scaffold diversification. Furthermore, studies on the intrinsic reactivity of 2-amino-4-arylpyridine N-oxides themselves are planned to explore their potential as novel synthetic scaffolds.