Cross couplings of O-peracylated 2,6-anhydro-aldose tosylhydrazones (C-(β-D-glycopyranosyl)formaldehyde tosylhydrazones) with alcohols, phenols, and carboxylic acids were studied under thermic or photolytic conditions in the presence of K₃PO₄ or LiOtBu. The reactions failed with EtOH, BnOH, or tBuOH, however, (CF₃)₂CHOH, electron poor phenols and carboxylic acids gave the corresponding C-β-D-glycopyranosylmethyl ethers and esters, respectively, representing a new access to these glycomimetic compounds.