Lithium cadmates bearing different ligands were compared with efficient (TMP)3CdLi (TMP = 2,2,6,6-tetramethylpiperidino) for their ability to deprotometalate anisole. The generated arylcadmates were evidenced using I 2. The results show that it is possible to replace only one of the TMP (with a piperidino, a diisopropylamino, a butyl, or a sec-butyl) without important yield drop. In the light of DFT calculations, reaction pathways were proposed for the deprotocadmations of anisole using a triamino, an alkyldiamino, and an aminodialkyl cadmate. © 2010 American Chemical Society.