Acetate Walking-Triggered Cycloaddition Cascades: Pd(0)-Catalyzed Access to syn-Dihydronaphthalenes via Ring Deletion and Orthogonal Esterification.

We report a Pd(0)-catalyzed cascade that enables the stereoselective synthesis of syn-1,4-dicarbinol dihydronaphthalene esters through regioterminal-selective acetate walking and tandem cycloaddition. The transformation proceeds via a palladium-catalyzed allylic transposition that generates a reactive diene intermediate in situ, which undergoes a rapid intramolecular [4+2] cycloaddition under mild conditions. Notably, the cascade incorporates a diastereoselective, acid-mediated ring deletion step coupled with orthogonal esterification, yielding highly functionalized syn-dihydronaphthalenes as a single diastereomer. This work establishes a unified catalytic platform that merges organometallic reactivity with cycloaddition chemistry, providing a concise and versatile entry into dihydronaphthalene architectures.