In situ generated catalytic systems based on copper or manganese salts in the presence of N-methylimidazole (NMI) efficiently converted BINOL into PXX. Copper-based catalysts completely consumed BINOL to give PXX as the only isolable product within 3h. When the copper salt/NMI catalyst was previously prepared the reaction consumed the BINOL within 2h. The manganese catalyst was slower but also completely consumed the BINOL within 9h.