Pd-Catalyzed tandem C−C/C−O/C−H single bond cleavage of 3-allyloxybenzocyclobutenols

A Pd-catalyzed sketal rearrangement of 3-allyloxybenzocyclobutenols was achieved, which involved successive proximal C−C bond cleavage, C−O bond cleavage and C−H bond allylic substitution. This methodology offered a novel approach to meta-β-keto phenols bearing an allylic group. Sequencial proximal or distal C−C bond cleavge/deallylation were also realized by tuning substituents on different positions of benzocyclobutenols.