The synthesis of carbohydrate-heterocycle hybrid molecules has led to several interesting biologically active products. In this work, we have developed an annulative process for the formation of novel C 2 -symmetrical 1,4-dioxane-carbohydrate hybrid compounds. Starting from simple sugars, original 6-6-6 heterocyclic frameworks were isolated. The dioxane units adopted a rare 1,4 twist-boat conformations in the liquid and solid-states. Synthetic derivatization allowed the preparation of C 2 -symmetrical glycomimetics that could be used for further biological investigations.