Asymmetric conjugate addition of alpha-heterosubstituted aldehydes such as a-amido and alpha-alkoxy aldehydes to vinyl sulfone was effected under the influence of structurally rigid trans-diamine-based Tf-amido organocatalyst (S,S)-2 with a dihydroanthracene framework to furnish a,a-dialkyl(amido)aldehydes and alpha,alpha-dialkyl-(alkoxy)aldehydes with high enantioselectivity. The chiral efficiency of the structurally unique catalyst (S,S)-2 is apparent in comparison with (S,S)-1 and (S,S)-4 with similar functionality.