Sequential Pd 0 ‐ and Pd II ‐Catalyzed Cyclizations: Enantioselective Heck and Nucleopalladation Reactions

Abstract An enantioselective consecutive cyclization/coupling process, catalyzed by palladium is reported. Stereoinduction arises from an enantioselective carbopalladation, generating an intermediate which promotes a nucleopalladation step. The dual cyclization sequence was compatible with a variety of alkyne‐tethered oxygen‐ and nitrogen‐centered nucleophiles, and a variety of alkenyl‐tethered aryl iodides, to forge numerous bisheterocycles in good yields and high regio‐ and enantioselectivities.