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Herein we report the first palladium-catalyzed intermolecular asymmetric allylic dearomatization reaction of β-naphthol derivatives to provide β-naphthalenones bearing an all-carbon quaternary center in good to excellent yields, chemoselectivity and enantioselectivity.[1] The reactions display a general scope for both β-naphthol derivatives and substituted allyl carbonates and offer a facile access to synthetically useful products, which are challenging to be obtained with known methods.