Synthesis of Furans/Pyrroles through Palladium‐Gold Relay Catalyzed Skeletal Editing of Carbonates or Carbamates <i>via</i> a Decarboxylative‐Aromatization Strategy

Abstract A novel Pd(0)/Au(I) relay catalysis strategy for converting propargylic cyclic carbonates into furans is reported. The method capitalizes on the sequential transformation of a palladium‐stabilized alkoxide‐π‐allyl intermediate into a gold‐stabilized dihydrofuran species, enabled by the cooperative action of palladium and gold catalysts. This approach is notable for its simplicity, broad functional group compatibility, and use of readily available substrates. By extending the methodology to five‐membered carbamates substrates, the construction of pyrrole frameworks is also demonstrated. Additionally, the method facilitates the synthesis of polycyclic furans and pyrroles via Diels‐Alder reactions, achieving high yields with excellent diastereoselectivities.