Competing diastereomeric TSs yielding the major and minor enantiomer of the branched product (R-prod and S-prod) differ by 3.1 kcal/mol, a predicted selectivity of 98.2% ee at 60 °C. These computational data are quantitatively consistent with experimental observations. Based on the computed PES, we predict that oxidative addition will occur reversibly such that the interconversion between intermediates int-1 and int-2 can occur from a prochiral starting material.