An efficient and convenient method was developed for the synthesis of novel 1,4-oxazepine- and 1,5-oxazocine-based sugar hybrids from readily available deoxysugar azides by means of tributylphosphine-mediated tandem reactions. The resulting glycoconjugates might be useful in increasing the diversity of sugar backbones, and could find applications as potential glycomimetics and in drug discovery.