Enantioselective Synthesis of Bicyclo[4.3.0]nonatrienones via Palladium-Catalyzed Desymmetric 1,5-Enyne Cycloisomerization

We herein disclose a palladium-catalyzed asymmetric desymmetric cycloisomerization of alkynyl-tethered cyclohexadienes, providing optically pure hydrindanes with one tertiary and one quaternary stereocenter. This reaction features a broad substrate scope, high atom economy, and good to excellent enantioselectivities. In addition, the diene and enone motifs embedded in the products offer synthetic handles for further structural diversification.