A naphthalene-based C-2-symmetric chiral diamine was obtained with high enantioselectivity by the double asymmetric addition of diethylzinc to 1,5-dibutoxynaphthalene-2,6-dicarbaldehyde followed by Mitsunobu azidation and the reduction of azide groups. The dynamic formation of an imine mixture between the enantiopure C-2-symmetric chiral diamine and 1,5-dimethoxynaphthalene-2,6-dicarbaldehyde afforded a chiral macrocyclic hexaimine composed of six naphthalene units, which can be reduced to the corresponding hexamine in high yield.