The use of 2-deoxy-2-trichloroacetamido-D-glucopyranose derivatives in syntheses of hyaluronic acid-related tetra-, hexa-, and octa-saccharides having a methyl beta-D-glucopyranosiduronic acid at the reducing end.
Expeditious and stereocontrolled syntheses are reported of beta-D-Glc pNAc-(1-->4)-[beta-D-Glc pA-(1-->3)-beta-D-Glc pNAc-(1-->4)]n-beta-D-Glc pA-(1-->OMe), where n = 1, 2, and 3, which represent structural elements of the extracellular polysaccharide hyaluronic acid. Condensation of 4,6-O-benzylidene-3-O-chloroacetyl-2-deoxy-2-trichloroacetamido- alpha-D-glucopyranosyl trichloroacetimidate with methyl (4-methoxyphenyl 2,3-di-O-benzoyl-beta-D-glucopyranosid)uronate gave the disaccharide derivative 9, which was demethoxyphenylated and imidoylated to afford the pivotal disaccharide trichloroacetimidate 7. Condensation of 7 with methanol followed by O-dechloroacetylation gave the acceptor 8. Coupling of 7 with 8 gave the tetrasaccharide derivative 4. O-Dechloroacetylation of 4 followed by condensation with imidate 7 afforded hexasaccharide 5, which was transformed into octasaccharide 6 by a similar two-step procedure. Subsequent O-dechloroacetylation, transformation of the N-trichloroacetyl groups into N-acetyl, debenzylidenation, and saponification of 4-6 afforded the tetra- (1), hexa- (2), and octa-saccharide (3) derivatives in high yields, as their sodium salts.
Blatter
G
G
Institut de Chimie Organique et Analytique, U.R.A. 499, Faculté des Sciences, Université d'Orléans, France.
Jacquinet
J C
JC
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D005960:Glucosides / Q000138:chemical synthesis* / Q000737:chemistry; D005965:Glucuronates / Q000032:analysis*; D006820:Hyaluronic Acid / Q000031:analogs & derivatives*; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000138:chemical synthesis* / Q000737:chemistry
D005960:Glucosides; D005965:Glucuronates; D009844:Oligosaccharides; D006820:Hyaluronic Acid