Herein, we report nickel(0) complexes equipped with a bulky chiral designer ligand enabling the fully atom-economic α-functionalization ketones with non-conjugated dienes under mild conditions (Fig. ). The construction of allylated quaternary centers proceeds with excellent levels of diastereo-and enantioselectivity. Isolation of the NHC-Ni(0) benzene complex and mechanistic studies paired with DFT calculations support a direct LLHT transfer of the αhydrogen atom of the ketone.