2,4-Dinitrobenzenesulfonamide-Directed S N 2-Type Displacement Reaction Enables Synthesis of β-d-Glycosaminosides.

An efficient protocol to construct β-d-gluco-/galactosaminosyl linkages was established using nonparticipating and strong electron-withdrawing C-2-2,4-dinitrobenzenesulfonamide (DNsNH)-directed SN 2-like glycosylation of glycosyl ortho-hexynylbenzoates. The reaction is applicable to a wide range of O-, N-, and C-nucleophiles and features convenient conversion of DNsNH into AcNH in high yield under mild conditions. Oligomerization-ready trisaccharide, composed of β-d-(1→3)-glucosamino residues, has been achieved, setting a solid foundation for the synthesis of oligosaccharides associated with Neisseria meningitidis capsular polysaccharide.