While important advances have been made in enantioselective intramolecular cyclization processes, the corresponding enantioselective intermolecular transformations have not been developed and represent an important gap in the field. To address this challenge, we report herein a method for the intermolecular enantioselective C-H alkylation of heteroarenes under mild conditions using a hindered NHC ligand with backbone chirality. An NHC ligand motif not previously utilized in enantioselective LLHT processes is paired with a strategy for the utilization of discrete 1,5-hexadiene-supported nickel(0) complexes to improve catalytic activity, increase functional group tolerance, and widen substrate scope of the transformation.