C2-symmetric 5-aza-semicorrins are readily prepared in enantiomerically pure form starting from pyroglutamic acid. Methylation at N(5) leads to neutral bidentate nitrogen ligands. Copper(I) and palladium(II) complexes of these ligands have proved to be efficient enantioselective catalysts for the cyclopropanation of olefins and for allylic nucleophilic substitutions.