Reaction of the 2-amino-2-methylpropandioicacidato anion (AMMA2-) with the Λ-β-[Co(R,R-picstien)Cl2]+ complex cation (R,R-picstien is 3R,4R-diphenyl-1,6-di(2-pyridyl)-2,5-diazahexane) results in displacement of the chloride ions with retention of absolute configuration of the metal atom and the bidentate AMMA2- stereospecifically adopting the β1 and stereoselectively the pro-S configurations. Decarboxylation of this complex in warm acidic solution produces a mixture comprising 93±3% Λ-β1-[Co(R,R-picstien)(R-ala)]2+ and 7±3% Λ-β1-[Co(R,R-picstien)(S-ala)]2+, as shown by NMR experiments. The chiral environment imposed on the prochiral AMMA2- fragment by the coordinated R,R-picstien ligand thus results in a stereoselective asymmetric synthesis of R-alanine in high enantiomeric excess. The crystal structure of the intermediate Λ-β1-[Co(R,R-picstien)(AMMA)]ClO4·2H2O complex has been determined at -135 °C. Crystal data: C30H35N5O10Cl1Co1 is orthorhombic, space group P212121, with a=9.598(2), b=11.964(2), c=26.477(3) Å and Z=4. The structure was refined by block-matrix least-squares methods to R=0.039 for 2622 diffractometer data. In the complex cation the bidentate AMMA2- fragment coordinates such that an internal hydrogen bond exists between the uncoordinated carboxyl group and one of the amine hydrogens of the central link, (NH···O 2.770(5) Å). This forces the coordinated amino acid intermediate to adopt the R (pro-S) configuration.