Herein we disclose a catalytic asymmetric dearomatization reaction of β‐naphthols with 4‐aryl‐1,2,4‐triazole‐3,5‐diones. A chiral phosphoric acid with spiro motif was found to be effective for this reaction. The chiral urazole embedded naphthalenones having both axial and central chirality were obtained in good to high yields (70–85%) with high diastereo‐ and enantioselectivities (>20:1, 8–96% ees), having C−N rotational energy barrier 31.54 K.Cal.mol−1 and t1/225 °C=589.8 years. The scope of the reaction was broad and few applications including a bromo‐amination reaction have been demonstrated.

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