In this report, synthesis of julolidines via one‐pot cascade reaction of aniline derivatives with a mixture of styrene and formaldehyde in the presence of silica sulfuric acid as an efficient catalyst has been studied under aerobic condition. By presented method, various julolidines are obtained under mild and transition metal‐free conditions. The reaction is proceeded with imine formation and followed by an Aza‐Diels‐Alder cycloaddition with styrene gave julolidine derivatives. The catalyst can be recycled and reused multiple times to catalyze the reaction.

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