Palladium-catalyzed asymmetric migratory diarylation of unactivated directing-group-free internal alkenes

Enantioselective dicarbofunctionalization of alkenes is a powerful strategy for constructing functionalized sp³-rich molecules, yet it remains challenging for unactivated substrates lacking directing groups. While asymmetric multicomponent reactions catalyzed by d¹⁰ transition metals have advanced for activated alkenes, enantioselective multicomponent cross-coupling of unactivated alkenes, particularly enabling remote functionalization to stereoselectively generate the nonadjacent stereocenters, is still underdeveloped. Herein, we report a palladium-catalyzed asymmetric migratory dicarbofunctionalization of directing-group-free, trisubstituted unactivated alkenes. This method forges remote stereogenic centers, enabling both 1,3-diarylation and 1,4-diarylation with high enantioselectivity and diastereoselectivity. Mechanistic studies indicate a chain-walking process involving irreversible Pd-H migration, rationalizing the observed regiocontrol. Enantioselective dicarbofunctionalization of alkenes is a powerful strategy for constructing functionalized sp³-rich molecules. Here, the authors report a palladium-catalyzed asymmetric migratory process that enables highly selective 1,3- and 1,4- diarylation of unactivated trisubstituted alkenes.