New enantiopure imines (1-9) with a chiral substrate to control the stereochemistry of a newly created stereogenic center have been synthesized by reaction of the commercially available (1R)-(-)-myrtenal and different primary amines. The diastereomerically enriched lithium-scorpionate compounds [Li(kappa(3)-mbpza)(THF)] (10) (mbpza = N-p-methylphenyl-(1 R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimeth ylpyrazol-1-y Dethylamide), [Li(kappa(3)-mobpza)(THF)] (11) (mobpza = N-p-methoxyphenyl-(1 Rand 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]2-hepten-2-yl]-2,2-bis(3,5-dimethy lpyrazol-1-ypethylamide), [Li(kappa(3)-fbpza)(THF)] (12) (fbpza = N-p-fluorophenyl-(1 R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-y1]-2,2-bis(3,5-dimeth ylpyrazol-1-yl)ethylamide), and [Li(kappa(3)-clbpza)(THF)] (13) (clbpza = N-p-chlorophenyl-(1 R and 1S)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-y1]-2,2bis(3,5-dimethy lpyrazol-1-ypethylamide) were obtained by a diastereoselective 1,2-addition of an organo lithium reagent to imines in good yield and with good diastereomeric excess (ca. 80%). The complexes [LiCI(kappa(2)-R,R-fbpzaH)(THF)] (14) and [LiCI(kappa(2)-R,R-clbpzaH)(THF)] (15) were obtained in enantiomerically pure form by the treatment of THF solutions of 12 or 13 with NH4Cl. The enantiomerically pure amines (R,R-mbpzaH) (16), (R,R-mobpzaH) (17), (R,R-fbpzaH) (18), and (R,R-clbpzaH) (19) were obtained by hydrolysis of the lithium-scorpionate compounds 10-13 with H2O. The lithium compound 12 was reacted with [TiCl4(THF)(2)] or [ZrCl4] to give the enantiopure complexes [MCl3(kappa(3)-R,R-fbpza)] [M = Ti (20), Zr (21)]. The amine compound 18 reacted with [MX4] (M = Ti, X = (OPr)-Pr-i, OEt; M = Zr; X = NMe2) to give the complexes [MX3(kappa(3)-R,R-fbpza)] (22-24). The reaction of Me3SiCl with [Zr(NMe2)(kappa(3)-R,R-fbpza)] (24) in different molar ratios led to the halide-amide-containing complexes [ZrCI(NMe2)(2)(kappa(3)-R,R-fbpza)] (25) and [ZrCl2(NMe2)(kappa(3)-R,R-fbpza)] (26) and the halide complex 21. The isolation of only one of the three possible diastereoisomers of complexes 25 and 26 revealed that chiral induction from the ligand to the zirconium center took place. The structures of these compounds were elucidated by H-1 and C-13{H-1} NMR spectroscopy, and the X-ray crystal structures of 5, 12, 14, 15, and 24 were also established.