Enzymatic transamination is catalyzed by pyridoxal/pyridoxamine, and it involves remarkable cooperative catalysis of a Lys residue in the transaminase. Inspired by transaminases, we developed a, class of axially chiral pyridoxamines 11 bearing a lateral amine arm. The pyridoxamines exhibited high catalytic activity and excellent enantioselectivity in asymmetric transamination of alpha-keto acids, to give various alpha-amino acids in 67-99% yields with.83-94% ee's. The lateral amine arm likely participates in cooperative catalysis as the Lys residue does in biological transamination and has an important impact on the transamination in terms of activity and enantioselectivity.