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Our results not only uncover the dual-character of surface hydroxyls in heterogeneous catalysis, but they also underline the significance of moderate moisture in the reaction system that may endow ceria catalysts with both good thermostability and high catalytic activity.Herein, we report a highly facile and unprecedented approach to synthesize congested N-(hetero)aryl amines en route to α-amino acid amides using α-bromoamides as alkylating agents under mild reaction conditions (room temperature). The involvement of aza-oxyallyl cations