(R)-1-Ferrocenylethyldimethylamine (III) was synthesized from acetylferrocene via a hydrogenative amination catalyzed with Pd/C and chemical resolution with (R)-(+)-tartaric acid. Lithiation of III with n-BuLi and following phosgenation with ClPPh2 provided (R)-N, N-dimethyl-(S)-1-(2-diphenylphosphinoferrocenyl)ethylamine (IV); (R) -1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyldi(3,5-dimethylphenyl)phosiphine (VIII) was obtained by treatment of IV with freshly prepared di(3,5-dimethylphenyl)phosphine through a configurationally retentive displacement in an overall yield of 19.5% calculated from acetylferrocene, The ee of which was about 95% according to the chiral HPLC analysis.