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Four galactofuranose-containing disaccharides have been prepared utilising various thioimidates [Galf-SC(NR)XR′] and suitably protected acceptors as key precursors. We observed that the efficiency of the coupling reactions was particularly dependent on the aglycon present on the furanosyl donor when copper(II) ions were used as the promoter, and that activation could be correlated with the nature of the third heteroatom, X.