Molecular iodine catalyzes acetalation and acetylation of reducing sugars and sugar glycosides with stoichiometric amounts of enol acetates under solvent-free conditions, thereby facilitating the synthesis of various types of orthogonally protected sugar derivatives in short time and good yields. The outcome of the reaction can be controlled by variation in temperature. Thus at lower temperature, it is possible to obtain the acetonide acetate as a single product whereas peracetate is the major product at higher temperature.