I. Sulfonium-Mediated Oxidative Glycosylation of Glycal Donors for the Synthesis of C(2)-Hydroxy-Beta-Glycosides. II. Hypervalent Iodine (iii)-Mediated Oxidative Glycosylation of Glycal Donors for the Synthesis of C(2)-Acyloxy-Beta-Glycosides. III. Efforts Toward the Synthesis of Immunologic Adjuvant Qs-21a(api)

263 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2003.Development of two novel glycosylation procedures, and the synthesis of immunologic adjuvant QS-21Aapi is reported. In the first glycosylation procedure, glycals were employed as glycosyl donors and activated with a reagent combination of diphenyl sulfoxide and triflic anhydride. This sulfonium-mediated oxidative glycosylation procedure can be used for 1,2-trans-C2-hydroxy-beta-glycoside synthesis with the application to assemble C2-branched oligosaccharides. In the second glycosylation procedure, glycals were activated with bisacyliodobenzene and boron trifluoride diethyl etherate for the synthesis of 1,2-trans -C2-acyloxy-beta-glycoside with the application to assemble non-C2-branched oligosaccharides. In the third section of this thesis, an acylated triterpene glycoside QS-21Aapi was targeted for synthesis using the two oxidative glycosylation procedures as well as a sulfonium-mediated dehydrative glycosylation procedure. Synthesis and extraction of the four components of the saponin, which includes a trisaccharide, a tetrasaccharide, a triterpene and an acyl side chain were accomplished leading to the assembly of these four components to provide the fully protected QS-21Aapi.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD