A catalyst system able to operate at temperatures as low as -65 degrees C for the Pd-catalyzed Kumada-Corriu cross-coupling reaction is described. This unprecedented level of activity allows the use of highly functionalized (Knochel-type) Grignard reagents. Additionally, the tolerance of the protocol toward a wide variety of functional groups allows for the synthesis of valuable compounds, including heterocyclic or polyfluoro biaryls.