ABSTRACT Fifteen novel ferrocene‐containing 5‐aminooxazoles were synthesized via an Ugi–Zhu multicomponent reaction, achieving an atom economy of 96% and isolated yields ranging from 24% to 68%. This protocol provides a rapid and efficient approach for generating structurally diverse ferrocenyl‐containing heterocycles under mild reaction conditions. The reactivity of these compounds toward maleic anhydride was investigated, involving an intermolecular aza‐Diels–Alder cycloaddition followed by intramolecular N‐acylation, decarboxylation, and dehydration, which would formally yield a pyrrolo[3,4‐ b ]pyridin‐5‐one core. However, as anticipated, this transformation was not observed experimentally. A metal–olefin complexation between the ferrocenyl moiety and the dienophile was hypothesized as the key factor governing the reactivity of the system. Thus, Density Functional Theory (DFT) based calculations were performed, and the computational results allow rationalizing for the first time why the interaction between ferrocenyl‐containing oxazoles and maleic anhydride gives rise to a highly stable charge‐transfer complex, consistent with a Dewar–Chatt–Duncanson‐type interaction, thereby strongly disfavoring the cycloaddition pathway. In this context, the ferrocenyl moiety becomes the region of highest electron density in the molecule, preventing the dienophilic site of the 5‐aminoxazole from participating in the cycloaddition and significantly altering the HOMO–LUMO distribution. These electronic and complexation effects account for the altered reactivity of the ferrocene‐containing heterocycles.