Therapeutic immunoadjuvants have been derived through a straightforward glycosylation of various alcohols with unprotected and non-activated monosaccharides, under solvent free conditions using ammonium chloride as a catalyst. Sugar acids such as glucuronic acid can be glycosylated without esterification and after acetylation yielded a novel 3,6-anhydro derivative. All the synthesized sugar glycosides were screened for immunomodulatory activities to be classified as immunostimulator, immunosuppressor, or immunoadjuvant against the weak antigen oval albumin (OVA). Most of the compounds revealed immunosuppressive (↓) or immunostimulatory (↑) activity with reference to lymphocyte proliferation and possess potential as vaccine adjuvants.