In this study, we successfully surmounted these problems to develop efficient iron-catalyzed AAPE reactions through C-H activation. We identified oxime ether , easily installed via the 15 condensation of N-methoxy amine with carbonyl in the presence of Lewis acids, as a multifunctional element. It serves as an effective directing group, an internal oxidant facilitating catalyst turnover, and the nitrogen source essential for azaoarene formation. An isobutyl aluminum(III) catecholate, easily generated by reacting commercially available triisobutylaluminum solution in toluene with one equivalent amount of catechol, acts as a base for deprotonative C-H activation, successfully suppressing undesired 20 C-H coupling with the base. As depicted in Figure for the hypothesized reaction mechanism, isobutyl catecholato aluminum(III) functions as a base. It facilitates the transmetallation of the alkyl group to Fe(III) and deprotonates the ortho-C-H bond, leading to the formation of isobutane and a ferracycle intermediate (I). The insertion of the alkyne into the Fe-C bond of intermediate I results in a sevenmembered ring ferracycle (II). This intermediate (II) then undergoes reductive elimination, yielding an N-methoxy pyridinium that acts as an oxidant, turning Fe(I) back to Fe(III). The oxophilic aluminum (III) captures the methoxy anion, preventing it from coordinating with Fe(III), which would otherwise poison the catalyst. The reaction is generally applicable for a variety of conjugated carbonyl compounds and a broad scope of alkynes including but-2-yne that produces methylated aza-arenes in high yields (vide infra), providing expedient access to π-extended aza-arenes to discover their utilities as electronic 5 materials . We anticipate the catechol effect discovered herein will be instrumental for the future development of other types of efficient iron-catalyzed C-H activation reactions.