Herein we have reported an expedient di-functionalization of such versatile scaffolds. By harnessing an under explored reactivity of N-aminopyridinium ylides, we have developed an aminopyridylation of N-substituted maleimides and 1, 4-quinones at room temperature in 2-methyl THF without any external reagents. The [3+2] cycloaddition of N-aminopyridinium ylides generate the corresponding cycloadduct with various maleimides and 1, 4-quinone substrates, which rapidly undergoes oxidation at the alkene moiety under open air, inducing a considerable driving force, thermodynamically, to facilitate aromatisation of the pyridine and a subsequent homolytic cleavage of the N−N bond to generate the desired 2, 3-aminopyridylated products in good to excellent yield. Experimental and computational studies clarify the reaction mechanism.