SYNTHESES OF D-GLUCOSAMINYL BOLAAMPHIPHILES

Twelve N-acetyl or NH2-free D-glucosaminyl bolaamphiphiles have been synthesized by the intermediate of N-allyloxycarbonyl-D-glucosaminyl precursors. Thus, glycosylation of alpha,omega-diols with 1,3,4,6-tetra-O-acetyl-2-allyloxycarbonyl-2-deoxy-beta-D-glucopyranose (1) gave the bis(glycosides) 2a-h in good yields and without column chromatography. Alkaline treatment of these derivatives followed by acetylation gave the peracetylated N-acetyl compounds 3a-h which were further deprotected by the Zemplen deacetylation procedure to the N-acetyl-D-glucosaminyl boiaamphiphiles 4a-h. The bis(glycosides) 2c,d,g were also transformed into the O-acetylated amino-free derivatives Sc,d,g by chemospecific deprotection of the N-allyloxycarbonyl groups with palladium (0). Further deprotection of the ester functions led to the completely deprotected bolaamphiphiles 7c,d,g with high yields. Fully deprotected compounds 7a,d,g,h were also obtained from 2a,d,g,h by alkaline treatment and purification by column chromatography. Surface tension measurements were realized for aqueous solutions containing the soluble bolaamphiphiles.