Stereospecific synthesis of the phosphono analogues of α- and β-D-glucose 1-phosphate

The present paper describes the convenient stereospecific synthesis of the analogues of α- and β-D-glucose 1-phosphate. The β analogue, (1-deoxy-β-D-glucopyranosyl)methanephosphonic acid, was synthesized by treatment of 2,6-anhydro-1-bromo-1-deoxy-3,4,5,7-tetra-O-acetyl-D-glycero-D-gluco-heptitol with triethyl phosphite, followed by deethylation of the obtained diethyl (1-deoxy-2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)methanephosphonate and deacetylation with ion-exchange resin. The a analogue, (1-deoxy-α-D-glucopyranosyl)methanephosphonic acid, was synthesized by starting from 2,3,4,6-tetra-O-benzyl-D-glucose through the following sequence: Wittig reaction with methylenetriphenylphosphorane, mercuriocyclization, bromodemercuriation, Arbuzov reaction, and removal of the protecting groups.