Fragments of Biopolymers Containing Glycosyl Phosphate Residues. 4. Synthesis of (12)-, (13 )- and (14)-Linked Glycosyl Phosphosugars by the Hydrogenphosphonate Method
A. V. Nikolaev, I. A. Ivanova, V. N. Shibaev, N. K. Kochetkov
N. D. Zelinsky Institute of Organic Chemistry Academy of Sciences of the USSR, Moscow
Abstract: Hydrogenphosphonate approach previously used for the 6-0-(glycosylphospho)-sugar synthesis is found to be efficient for the synthesis of (12)-, (13)-, and (14)-linked mannosyl phosphomannoses which may serve as models for various fragments of natural poly(glycosyl phosphates). Glycosylphosphitylation of suitable monohydroxyl derivatives with 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl H-phosphonate in pyridine in the presence of Me3CCOCl, followed by oxidation of the H-phosphonate diesters obtained (I2 in PyH20), resulted in fully protected phosphate diesters in 7087% yields. Deprotection of these derivatives by standard procedures lead to deblocked glycosyl phosphosugars. The data of 1H, 13C, and 31P NMR spectra of the synthesized, phosphate diesters are discussed.
Russian Journal of Bioorganic Chemistry 1990, 16 (5):674-684