With the potential utility of the VLAO method proved by reproducing the reported ligand engineering processes, we then performed the experimental validation of the VLAO method. For this purpose, we have focused on the palladium-catalyzed hydrogermylation of ynamide 9 reported by Blanchard, Houk, Bizet and coworkers. The hydrogermylation of 9 affords two regioisomeric products, namely α-product 10 and β-product 11, and the regioselectivity can be controlled by ligands (Figure ). For example, hydrogermylation of 9a using bis [2-(diphenylphosphino)phenyl] ether (DPEPhos) affords the α-product selectively, whereas the β-product is exclusively formed when PMe t Bu2 is employed as the ligand. On the contrary, hydrogermylation of 9b, which has a terminal alkyne moiety, tends to give the β-product preferentially, and, to the best of our knowledge, no α-selective ligands have been reported. Hence, we aimed to find α-selective ligands by the VLAO method. First, using the virtual ligand reproducing PPh3, selectivity-determining TSs, namely α-TS and β-TS, were calculated, and the α selectivity 𝜉 W was estimated to be 40.7%. according to the following equation: