As ambitioned, the chiral azo compounds were transformed to chiral amines through a simple Raney-Ni reduction at room temperature, where the respective chiral amine 38 was obtained in 67% yield and 97.0:3.0 e.r. (Figure ). The amine 38 was further modified to the chiral urea analogue 39, which allowed the determination of the absolute configuration by single crystal X-ray crystallographic analysis. (Figure ). In order to gain insights into the observed enantioselectivity, DFT calculations were performed for the migratory insertion elementary step in the presence of the preligand L12 (Figure ). Calculations revealed that the major enantiomer was energetically favored over the minor enantiomers by 3.8 kcal mol -1 , which is in agreement with the experimental findings (see Supporting Information for details).