Novel tetranuclear copper |2 + 4| cubanes 1 and 2 have been synthesized from the reaction of hydrated copper salts/precursors with N,O chelating β-ketoaminato ligands. Creation of 1 and 2 occurs by in situ generation of the tridentate chelating species HL1O(2-) via copper mediated C-O bond formation and dearomatization of H3L1, while anhydrous salts afforded mononuclear complex 3.