The strong directing ability of the N,N,N′,N′-tetramethyldiaminophosphorodiamidate group has been used to achieve selective metalations on various heterocycles such as pyridines, quinolines and quinoxalines with TMP-derived bases like TMPMgCl·LiCl, TMP_2Mg·2LiCl, and TMP_2Zn·2MgCl_2·2LiCl. This protocol was applied in the synthesis of etoricoxib, talnetant and a P-selectin inhibitor.