120403-27-2

Upstream product

• 87470-73-3 phenyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 
• 108-24-7 acetic anhydride 
• 4356-77-8 1,6-di-O-acetyl-2,3,4-tri-O-benzyl-D-glucopyranose 
• 882-33-7 diphenyldisulfane 
• 2936-70-1 (2R,3S,4S,5R,6S)-2-Hydroxymethyl-6-phenylsulfanyl-tetrahydro-pyran-3,4,5-triol 
• 210834-01-8 phenyl 6-O-trityl-1-thio-β-D-glucopyranoside 
• 861927-81-3 phenyl 2,3,4-tri-O-benzyl-1-thio-6-O-trityl-β-D-glucopyranoside 
• 13992-16-0 (2R,3R,4S,5R,6S)-2-(acetoxymethyl)-6-(phenylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate 
• 6564-72-3 2,3,4,6-tetra-O-benzyl-D-glucopyranose 
• 4356-77-8 acetyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranoside 
• 108-98-5 thiophenol 
• 120403-26-1 phenyl 2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside 
• 100-44-7 benzyl chloride 
• 10548-46-6 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose 

Downstream Products

• 130144-08-0 methyl 2-O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-3-O-benzyl-4,6-O-benzyliden-α-D-glucopyranoside 
• 244286-92-8 methyl 2,3,4-tri-O-benzyl-6-O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-β-D-glucopyranoside 
• 120444-53-3 6-O-acetyl-2,3,4-tri-O-benzyl-β-D-glucopyranosyl chloride 
• 120403-33-0 phenyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside 
• 120403-31-8 phenyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside 
• 38184-16-6 phenyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 
• 120403-28-3 phenyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 
• 120403-35-2 O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-β-D-glucopyranosyl chloride 
• 709668-20-2 allyl 2,3,4-tri-O-benzyl-α-D-glucopyranosyluronate-(1->3)-2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 
• 709668-19-9 allyl 2,3,4-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 
• 709668-18-8 allyl 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl-(1->3)-2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 
• 130050-87-2 methyl O-(3,4,6-tri-O-acetyl-2-chloroacetamido-2-deoxy-β-D-glucopyranosyl)-(1->6)-O-(2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->2)-3-O-benzyl-4,6-O-benzylidene-α-glucopyranoside 
• 118266-82-3 methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-α-D-glucopyranoside 
• 158411-91-7 (2S,3S,4S,5R,6S)-3,4,5-Tris-benzyloxy-6-((3R,4R,5S,6S)-2,4,5-tris-benzyloxy-6-methyl-tetrahydro-pyran-3-yloxy)-tetrahydro-pyran-2-carboxylic acid methyl ester 

Relevant academic research and scientific papers

Rapid Synthesis of l-Idosyl Glycosyl Donors from α-Thioglucosides for the Preparation of Heparin Disaccharides

A new methodology for the synthesis of the most challenging heparin building block has been developed. Orthogonally protected l-idosyl glycosyl donors were prepared by C5 epimerization of the corresponding thioglucosides using the hydroboration/oxidation method followed by a 4,6-acetal formation. The α-anomeric configuration was crucial, and the bulky C4 substituent was advantageous for the high l-ido diastereoselectivity. The 4,6-arylmethylene group proved to be a directing element in glycosylation, whereby stereoselective α-idosylation could be achieved by using idosyl donors without a C-2 participating group.

Novel approaches for the synthesis and activation of thio- and selenoglycoside donors

(Chemical Equation Presented) Alkyl thio-, phenyl seleno-, and phenyl thioglycosides can be prepared through short synthetic sequences based on the generation of glycosyl iodides as versatile intermediates. In addition, a novel cheap combined system (stoichiometric NBS and catalytic Bi(OTf)3) has been developed for rapid and efficient activation of a wide variety of thio- and selenoglycoside donors.

Synthesis of cis-(1 → 3)-glycosides of allyl 2-acetamido-4,6-O- benzylidene-2-deoxy-α-D-glucopyranoside

Syntheses of allyl 2,3,4-tri-O-benzyl-α-D-gluco- and D-galactopyranosyluronate-(1→3)-2-acetamido-4,6-O-benzylidene-2-deoxy- α-D-glucopyranoside via oxidation of the hydroxymethyl group of allyl 2,3,4-tri-O-benzyl-α-D-gluco- and D-galactopyranosyl-(1→3)-2-

Synthesis and absolute configuration of lepidimoide, a high potent allelopathic substance from mucilage of germinated cress seeds

Lepidimoide (1), 1,2-cis-linked dissacharide, was synthesized from D-glucose and α-L-rhamnose for determination of the absolute configuration.

Use of the methylsulfenyl cation as an activator for glycosylation reactions with alkyl (aryl) 1-thioglycopyranosides: synthesis of methyl O-(2-acetamido-2- deoxy-beta-D-glucopyranosyl)-(1----6)-O-alpha-D-glucopyranosyl-(1----2) -alpha-D -glucopyranoside, a derivative of the core trisaccharide of E. coli K12.

Methylsulfenyl bromide (MSB) and methylsulfenyl trifluoromethanesulfonate (MST) have been used to prepare 1,2-cis-linked disaccharides. Ethyl (phenyl) 1-thio-beta-D-gluco- and galacto-pyranosides having non-participating (benzyloxy) protecting groups were used as the donors. The alpha beta-ratio of the products depended on the promoter and conditions of reaction. Intimate ion-pairs, formed initially, may be responsible for the steric outcome of the glycosylations. Thus, with ethyl 2,3,4,6-tetra-O-benzyl-alpha-D-mannopyranoside as a donor, moderate quantities of the beta-linked disaccharide could be produced using MSB as the activator. The synthesis of the title trisaccharide glycoside that contains 1,2-cis and 1,2-trans-linkages is described.

SYSTEMATIC CHEMICAL SYNTHESIS AND N.M.R. SPECTRA OF METHYL α-GLYCOSIDES OF ISOMALTO-OLIGOSACCHARIDES AND RELATED COMPOUNDS

Acid-catalyzed thiophenolysis of 1,6-anhydro-2,3,4-tri-O-benzyl-β-D-glucopyranose and acetylation of the resulting phenyl 2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside (4) gave phenyl 6-O-acetyl-2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside (5).Reaction of 5 with chlorine gave, stereospecifically, the corresponding β-glycosyl chloride, which was treated with 4 in the presence of silver perchlorate and 2,4,6-trimethylpyridine to afford phenyl O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-1-thio-α-D-glucopyranoside (17).Crystalline O-(6-O-acetyl-2,3,4-tri-O-benzyl-α-D- glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-β-D-glucopyranosyl chloride, readily obtainable in a stereospecific manner from 17 by treatment with chlorine, was used as the key glycosyl (isomaltosyl) donor in the bockwise synthesis of methyl glycosides of isomalto-oligosaccharides, up to and including the octasaccharide.The methyl α-glycoside of isomaltotetraose fluorinated at C-6 of the terminal D glucopyranosyl group was prepared by using SnCl2-activated 2,3,4-tri-O-benzyl-6-deoxy-6-fluoro-α,β-D-glucopyranosyl fluoride as the glycosyl donor, a suitably protected methyl α-isomaltotrioside as the nucleophile, and silver perchlorate as the promoter.The n.m.r. spectra (1H- and 13C-) of numereous synthetic intermediates were analyzed and completely assigned by a variety of two-dimensional homo- and hetero-nuclear n.m.r.-spectroscopic techniques, and the final deprotected title oligosaccharides were characterized by 13C-n.m.r. data.Silver perchlorate-mediated glycosylation reactions involving β-glycosyl chlorides were high-yielding and showed high stereoselectivity for the formation of an α-(cis)-glycosidic linkage.The practical limitation of obtaining high isomalto-oligosaccharides in this way appears to lie solely in the separation technique applied for the resolution of the crude products formed.