Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols via Tandem Etherification/Claisen Rearrangement

Transition metal-catalyzed asymmetric allylic dearomatization of β-naphthols provides efficient access to enantioenriched naphthalenones. However, these reactions generally suffer from limited substrate scope, incompatibility with alkyl-substituted allylic electrophiles, and poor understandings of the reaction mechanism. Herein, we report a rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols utilizing a bisdihydrobenzooxaphosphole (BIBOP) chiral ligand. This catalytic system displays high yields and enantioselectivity and broad substrate scope, efficiently accommodating both alkyl- and aryl-substituted allylic carbonates. Detailed mechanistic studies reveal that the reaction proceeds through a tandem asymmetric allylic etherification/Claisen rearrangement sequence. This provides critical insights into the fundamental pathways for the asymmetric allylic dearomatization of naphthols.