An access to various sulfation patterns in dermatan sulfate: chemical syntheses of sulfoforms of trisaccharide methyl glycosides.
The syntheses are reported for the first time of alpha-L-IdopA2SO(3)-(1-->3)-beta-D-GalpNAc4SO(3)-(1-->4)-alpha-L-IdopA2SO(3)-(1-->OMe), its disulfated analogue alpha-L-IdopA2SO(3)-(1-->3)-beta-D-GalpNAc-(1-->4)-alpha-L-IdopA2SO(3)-(1-->OMe), and of beta-D-GalpNAc4SO(3)-(1-->4)-alpha-L-IdopA2SO(3)-(1-->3)-beta-D-GalpNAc4SO(3)-(1-->OMe), which represent structural fragments of dermatan sulfate, unavailable directly by chemical or enzymatic degradation of the glycosaminoglycan polymer. These molecules were readily obtained from a pair of key disaccharide intermediates, in which the relative difference of stability of the D-GalNAc 4-hydroxy protecting groups (acetate or pivalate) toward saponification conditions allowed access to various sulfoforms from a common precursor. For the preparation of these blocks, the 4-O-pivaloyl-D-galacto moiety was readily obtained through a one-pot stereospecific intramolecular nucleophilic displacement on an easily available 3-O-pivaloyl-D-gluco precursor, and the L-IdoA moiety through selective radical oxidation at C-6 of a L-ido 4,6-diol derivative with oxoammonium salts.
Barroca
Nadine
N
Institut de Chimie Organique et Analytique, UFR Faculté des Sciences, UMR CNRS 6005, Université d'Orléans, BP 6759, F-45067 Orléans, France.
Jacquinet
Jean-Claude
JC
D002236:Carbohydrate Conformation; D003871:Dermatan Sulfate / Q000737:chemistry*; D004187:Disaccharides / Q000138:chemical synthesis / Q000737:chemistry; D006031:Glycosylation; D008759:Methylglycosides / Q000138:chemical synthesis / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D013431:Sulfates / Q000737:chemistry; D014312:Trisaccharides / Q000138:chemical synthesis* / Q000737:chemistry
D004187:Disaccharides; D008759:Methylglycosides; D013431:Sulfates; D014312:Trisaccharides; C476423:methyl 2-sulfoidouronosyl-1-3-N-acetyl-4-sulfogalactopyranosyl-1-4-2-sulfoidopyranoside; C476424:methyl 2-sulfoidouronosyl-1-3-N-acetylgalactopyranosyl-1-4-2-sulfoidopyranoside; C476425:methyl N-acetyl-4-sulfogalactopyranosyl-1-4-2-sulfoidopyranoside-1-3-N-acetyl-4-sulfogalactopyranoside; D003871:Dermatan Sulfate