The 2,2,6,6-tetramethylpiperidyl (TMP) bases TMPMgCl.LiCl and (TMP)2Zn.2MgCl2.2LiCl have found application in the regioselective deprotometalation of diverse substrates.1 The obtained functionalized molecules via such strategy can be further employed in the construction of potential bioactive heterocycles. Fluorinated nitriles are valuable building blocks for the synthesis of important N-heterocyclic motifs such as benzo[d]imidazo[2,1-b]thiazoles,2 indazole,3 and dibenzoxazepinamines.4 Therefore, considering the ortho¬-directing properties of fluoro and cyano groups from these nitriles and their synthetic applicability in heterocyclic chemistry, we decided to assess their selective metalation with TMPMgCl.LiCl and (TMP)2Zn.2MgCl2.2LiCl and sequential functionalization with various electrophiles. We obtained 47 highly functionalized nitriles with the exploration of new and scarcely studied metalation sites (See Scheme 1 for examples). The yields ranged from 48 to 95%. Additionally, we performed a difunctionalization of 4-fluorobenzonitrile leading to 2f (80% yield) and used 2l as building block for the synthesis of the dibenzoxazepinamine 3 (84% yield), respectively.