Enantioselective Synthesis of Hydrindanes via Palladium-Catalyzed Asymmetric Desymmetrization of Cyclohexadiene Derivatives

We herein disclose a strategy for the asymmetric desymmetrization of cyclohexadiene derivatives via a palladium-catalyzed Heck and tandem Heck/Tsuji-Trost allylic alkoxylation reaction. By employing DCE as the solvent, we obtained a variety of chiral hydrindanes containing an all-carbon quaternary carbon center and a tertiary carbon chiral center in good yields with excellent enantioselectivities. With alcohols as the solvent, the valuable chiral hydrindanes with one quaternary stereocenter and two tertiary centers were constructed with a high level of enantioinduction.