The TBOxCr(III)Cl/TBOxCr(II) system is ideal for catalytic asymmetric redox process. Because of the electron density of the TBOxH ligand high turnover numbers are expected, hence allowing decrease in the chromium catalyst loadings and acceleration of the reaction rate. High reactivity and high diastereo-/ enantioselectivity are shown in asymmetric pinacol coupling reactions of aldehydes, asymmetric NH allylation reaction of aldehydes, asymmetric allenylation reactions of aldehydes, and some other reactions. These proceed exceedingly efficiently catalyzed by the TBOxCr(III)Cl redox system due to the well-designed chiral environment of the ligands and the cis-beta configuration of the center Cr metal.