Biphenyl-based phosphine ligands can be prepared on a significantly larger scale than previously possible as a result of the following discoveries and improvements to the original experimental procedure: the finding that CuCl catalyzes the coupling of hindered dialkylchlorophosphines with Grignard reagents; the development of conditions that permit ClPCy2 to be prepared and utilized in situ; the development of a more reliable large-scale preparation of 2-dimethylaminophenylmagnesium halide.