Synthesis of part of a proposed insulin second messenger glycosylinositol phosphate and the inner core of glycosylphosphatidylinositol anchors

Abstract Synthesis of 6- O -(2-amino-2-deoxy-α-D-glucopyranosyl)-D- myo -inositol 1-phosphate, an inner core structure found in various glycosylphosphatidylinositols, and the corresponding 1,2-cyclic phosphate, proposed as part of an insulin second messenger glycosylinositol phosphate, is described. Chirality in the inositol part of the molecule was achieved by the use of a known D-camphor acetal intermediate. The glycosylation used 4- O -allyl-2-azido-3,6-di- O -benzyl-2-deoxy-α-D-glucopyranosyl fluoride as glycosyl donor. The allyl group can be chemoselectively removed, opening a route to oligosaccharides bound to the 4-position of the glucosamine unit. The phosphorylation was accomplished by the phosphoramidate procedure.