Palladium-Catalyzed α‑Arylation of Cyclic Vinylogous Esters for the Synthesis of γ‑Arylcyclohexenones and Total Synthesis of Aromatic Podocarpane Diterpenoids

Described is a method for the formal γ-arylation of cyclohexenones allowing synthesis of a remote all-carbon quaternary center. The process involves the palladium-catalyzed α-arylation of a α-substituted cyclic vinylogous ester followed by the Stork–Danheiser transposition. The synthetic utility of this protocol is featured in the total syntheses of (±)-12-hydroxy-13-methyl­podocarpa-8,11,13-trien-3-one, (±)-3β,12-dihydroxy-13-methyl­podocarpane-8,11,13-triene, and (±)-O-methyl nimbinone.