A series of 2-(cyanomethyl)azaarenes containing benzothiazole or benzoxazole were designed and synthesized for asymmetric α-functionalization with N-Boc-amino sulfones. The Mannich adducts were obtained in high yields with good diastereo- and enantioselectivities. Aryl-substituted amino sulfones were tolerated under the current conditions, and the reaction can be performed on gram scale in good results.