Accessing Unsymmetrically Linked Heterocycles through Stereoselective Palladium‐Catalyzed Domino Cyclization

Abstract A palladium‐catalyzed strategy is presented to synthesize unsymmetrically linked heterocycles within stereoselective tetrasubstituted olefins. This reaction is proposed to occur via a vinyl‐Pd II intermediate capable of initiating the cyclization of various alkyne‐tethered nucleophiles. Products are formed in up to 96 % yield and excellent stereoselectivities are obtained using low catalyst loadings. This transformation was scalable up to 1 mmol and mechanistic studies suggest a syn ‐carbopalladation of the carbamoyl chloride followed by Pd II ‐catalyzed cyclization of alkyne‐tethered nucleophiles.