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

• Published in: Tetrahedron 1997-12, Vol.53 (52), p.17727-17734
• Main Authors: Garegg, Per J., Konradsson, Peter, Oscarson, Stefan, Ruda, Katinka
• Format: Article
• Language: English
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/S0040-4020(97)10238-1

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. Synthesis of 1, an inner core structure found in various glycosylphosphatidylinositols, and the corresponding 1,2-cyclic phosphate 2, proposed as part of an insulin second messenger glycosylinositol phosphate, is described.