AbstractMetalation of 2,4‐dicyanocubanecarboxamide (4) with lithium tetramethylpiperidide (LiTMP) followed by quenching with CO2 is non‐regioselective and results in carboxylation at the 3 (→ 5) and 6 (→ 6 ) positions. However, when the reaction was repeated with LiTMP pre‐treated with more than 0.5 equivalent of MgBr2, only 6 was produced. This was shown to occur by direct, regiospecific ortho‐magnesiation by the bases BrMgTMP and MgTMP2. This initial observation of ortho‐magnesiation has opened the way to wide application of this new methodology, a valuable and useful complement to ortho‐lithiation.