Planar chiral monodentate 1,3-disubstituted ferrocene phosphines inspired on JohnPhos-type ligands have been synthesized and applied to the enantioselective gold(I) catalyzed [4 + 2] cycloaddition of 1,6-arylenynes. Computational studies rationalized the working mode of the catalyst on the folding of the substrate in the chiral environment of the ligand involving attractive noncovalent interactions.