We performed quantum chemical calculations using the VL to check if this ligand engineering can be reproduced by the VLAO method (Figure ). In this case, to approximate dppe-type ligands by a virtual ligand, 1,2-bis(dichlorophosphino)ethane was used as the dummy moiety, and the penalty functions (the keep potential, the keep angle potential and the ovoid LJ potential) were added to four Cl atoms. Firstly, to reproduce dppe with thus-prepared virtual ligand, geometry optimizations of the palladium(II) complex 4 and TS45 were performed using the VL parameters tuned to reproduce PPh3 (pVL Ph ). As a result, the activation energy (ΔE ‡ ) was calculated to be 36.1 kcal/mol which is consistent with the value calculated using the actual dppe molecule (Figure , 35.4 kcal/mol). We then performed the differentiation of the electronic energy of 4 and TS45, and the derivative values of the activation energy (ΔE ‡ ) was calculated (see SI for the detailed formulation). The derivative values with respect to parameters a1, a2, b1, b2, c1, c2 and 𝑟 7 were shown in Figure (right). As for the electronic parameter (r0), a large negative derivative value was obtained. Because an increase of 𝑟 7 value makes the VL electron-deficient (see Figure ), this result is consistent with the third criterion for the ligand design by Schoenebeck and coworkers (see above). Regarding the steric parameters (a1, a2, b1, b2, c1 and c2), small negative derivative values were computed, implying that increase of steric bulk would slightly decrease the activation energy. Because the first and second criteria for the ligand design would generally demand opposite steric features (see above), the small absolute values for steric parameters might be a result of the cancelling out of these irreconcilable effects.