Direct and selective mono-N-pyridylation of trans-(R,R)-cyclohexane-1,2- diamine is described here. Facile preparation of a novel chiral 2-aminoDMAP core catalaphore via Cu catalysis has led to the development of various sulfonamide/2-aminoDMAPs as bifunctional acid/base organocatalysts (most in two steps overall), which have been shown to very effectively promote asymmetric conjugate addition of acetylacetone to trans-β-nitroolefins with good to excellent yields (87-93%) and enantioselectivites (up to 99%). © 2013 American Chemical Society.