The diastereoselective addition of higher order (H.O.) cuprates and zinc-copper reagents to aliphatic and aromatic chiral imines derived from (S)-1-phenylethylamine was examined. Aliphatic chiral imines react with (Allyl) 2 CuCNLi 2 and (n-Bu) 2 Cu(CN)Li 2 in the presence of BF 3 .Et 2 O and Me 3 SiCl in high diastereoselection, while c-C 6 H 1 1 Cu(CN)ZnI and AllylCu(CN)ZnBr afford chiral amines in comparable yields without additives. Moreover the synthesis of a key intermediate towards a δ-amino-acid was reported.