Intermolecular asymmetric functionalization of unstrained C(sp³)–C(sp³) bonds in allylic substitution reactions

Catalytic asymmetric functionalization of unstrained C(sp³)–C(sp³) bonds is a promising strategy to edit the structure of a molecule stereoselectively, but such reactions are rare. Existing methods for the catalytic functionalization of C–C bonds typically involve C–C bonds in strained structures. Here we report a strategy to achieve unexplored enantioselective functionalizations of allylic C(sp³)–C(sp³) bonds. Protocols for both kinetic resolution and dynamic kinetic asymmetric transformation are established to construct new C–C bonds at the position of a C(sp³)–C(sp³) bond in the reactant. This study shows that enantioselective functionalizations can be achieved even at unstrained C–C bonds, and an alkyl C–C bond can also work as a leaving group instead of a stable product in enantioselective allylic substitution reactions. Mechanistic experiments and density functional theory calculations reveal that deracemization by the formation of dienes enables the process to occur as a dynamic kinetic asymmetric transformation.