An enantioselective approach for synthesizing fluorinated azaarenes containing vicinal quaternary-tertiary stereocenters is summarized. The chiral copper(I)-phosphine complex binds with the azaarenes followed by Michael addition to unsaturated acyl imidazoles, resulting in α-functionalized products with an excellent level of enantioselectivities (up to 99%), diastereoselectivities (>20:1), and yields (up to 97%). Furthermore, post-functionalization of the acyl imidazole part has also been demonstrated.