methyl 2-acetamido-4-S-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-2-deoxy-4-thio-β-D-glucopyranoside | 176690-95-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-4-S-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-2-deoxy-4-thio-β-D-glucopyranoside
• 英文别名: N-[(2R,3R,4R,5S,6R)-5-[(2S,3R,4R,5S,6R)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]sulfanyl-4-hydroxy-6-(hydroxymethyl)-2-methoxyoxan-3-yl]acetamide
• CAS: 176690-95-2
• 化学式: C₁₇H₃₀N₂O₁₀S
• 分子量: 454.499
• InChiKey: HQLJJSMBFWKICQ-GBZYHGPESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.4
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  212
• 氢给体数：
  7
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 methyl 2-acetamido-4-S-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-2-deoxy-4-thio-β-D-glucopyranoside 在 吡啶 作用下， 生成 Acetic acid (2R,3S,4R,5R,6R)-2-acetoxymethyl-5-acetylamino-3-((2S,3R,4R,5S,6R)-4,5-diacetoxy-6-acetoxymethyl-3-acetylamino-tetrahydro-pyran-2-ylsulfanyl)-6-methoxy-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  Stereoselective synthesis of N-acetyl thiochitooligosaccharides. Different behaviours of methyl N-acetyl-α- and -β-thiochitobiosides during acetolysis

  摘要：

  A stereoselective synthesis of N-acetyl-thiochito-di-, -tri- and -tetra-saccharides is described. Coupling of methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-triflyl-beta-4 or -alpha-D-galactopyranoside 19 with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio- beta-D-glucopranose 5 in the presence of cysteamine in DMF gave, after de-O-acylation, methyl N,N'-diacetyl-beta- 9 and -alpha-thiochitobioside 21, respectively. Different behaviours of peracetylated methyl beta- 10 and alpha-thiochitobioside 22 towards acetolysis with Ac2O-AcOH-H2SO4 solution were observed, with the beta-isomer giving acyclic sugar species together with the desired thiochitobiose peracetate 11, while the alpha-isomer gave exclusively the thiochitobiose peracetate 11. This remarkable difference between alpha- and beta-glycosides was further demonstrated by comparative acetolysis of methyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha- 23 and -beta-D-glucopyranoside 24. Methyl N,N',N ''-triacetylthiochitotriosides 29 and 30 were synthesized through conversion of N,N'-diacetylthiochitobiose peracetate 11 into N,N'-diacetyl-1,4-dithiochitobiose derivative 28, followed by its coupling with triflates 4 and 19 in the presence of cysteamine. Similarly, extension of the sugar chain to a higher homologue was achieved by converting methyl N,N',N ''-triacetylthiochitotrioside 30 into the N,N',N ''-triacetyl-1,4,4'-trithiochitotriose derivative 33, the coupling of which with triflate 19 in the presence of cysteamine provided the methyl N,N',N '',N triple prime-tetraacetylthiochitotetraoside 34 after de-O-acylation.

  DOI：

  10.1039/p19960000581
• 作为产物：
  描述：

  2-acetamido-3,4,6-tri-O-acetyl-1-S-acetyl-2-deoxy-1-thio-β-D-glucopyranose 在 1,4-dithio-erythritol 、 sodium methylate 、 巯基乙胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 2-acetamido-4-S-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-2-deoxy-4-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Stereoselective synthesis of N-acetyl thiochitooligosaccharides. Different behaviours of methyl N-acetyl-α- and -β-thiochitobiosides during acetolysis

  摘要：

  A stereoselective synthesis of N-acetyl-thiochito-di-, -tri- and -tetra-saccharides is described. Coupling of methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-triflyl-beta-4 or -alpha-D-galactopyranoside 19 with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio- beta-D-glucopranose 5 in the presence of cysteamine in DMF gave, after de-O-acylation, methyl N,N'-diacetyl-beta- 9 and -alpha-thiochitobioside 21, respectively. Different behaviours of peracetylated methyl beta- 10 and alpha-thiochitobioside 22 towards acetolysis with Ac2O-AcOH-H2SO4 solution were observed, with the beta-isomer giving acyclic sugar species together with the desired thiochitobiose peracetate 11, while the alpha-isomer gave exclusively the thiochitobiose peracetate 11. This remarkable difference between alpha- and beta-glycosides was further demonstrated by comparative acetolysis of methyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha- 23 and -beta-D-glucopyranoside 24. Methyl N,N',N ''-triacetylthiochitotriosides 29 and 30 were synthesized through conversion of N,N'-diacetylthiochitobiose peracetate 11 into N,N'-diacetyl-1,4-dithiochitobiose derivative 28, followed by its coupling with triflates 4 and 19 in the presence of cysteamine. Similarly, extension of the sugar chain to a higher homologue was achieved by converting methyl N,N',N ''-triacetylthiochitotrioside 30 into the N,N',N ''-triacetyl-1,4,4'-trithiochitotriose derivative 33, the coupling of which with triflate 19 in the presence of cysteamine provided the methyl N,N',N '',N triple prime-tetraacetylthiochitotetraoside 34 after de-O-acylation.

  DOI：

  10.1039/p19960000581

文献信息

• Synthesis and conformational analysis of glycomimetic analogs of thiochitobiose
  作者：Anja Fettke、Dirk Peikow、Martin G. Peter、Erich Kleinpeter

  DOI：10.1016/j.tet.2009.03.067

  日期：2009.5

  The synthesis of six analogs of N,N'-diacetylchitobiose is reported, including a novel transglycosylation reaction for the preparation of S-aryl thioglycosides. The conformations of the compounds were studied by a combination of NMR spectroscopy and molecular modeling, using force field calculations. In the case of the S-aryl thioglycosides with exclusively S-glycosidic linkages, dihedral angles of the disaccharidic S-glycosidic bonds, Phi' and Psi' and of the S-arylglycoside bonds, Phi and Psi, were found to be similar, whereas they were different in mixed glycosides and in a thiazoline derivative. An adequate correlation between the calculated H,H-distances of the local minima and the measured NOE contacts was achieved by applying population-weighted averages over participating conformers based on weighted relative energies. (C) 2009 Elsevier Ltd. All rights reserved.
• Stereoselective synthesis of N-acetyl thiochitooligosaccharides. Different behaviours of methyl N-acetyl-α- and -β-thiochitobiosides during acetolysis
  作者：Lai-Xi Wang、Yuan C. Lee

  DOI：10.1039/p19960000581

  日期：——

  A stereoselective synthesis of N-acetyl-thiochito-di-, -tri- and -tetra-saccharides is described. Coupling of methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-triflyl-beta-4 or -alpha-D-galactopyranoside 19 with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio- beta-D-glucopranose 5 in the presence of cysteamine in DMF gave, after de-O-acylation, methyl N,N'-diacetyl-beta- 9 and -alpha-thiochitobioside 21, respectively. Different behaviours of peracetylated methyl beta- 10 and alpha-thiochitobioside 22 towards acetolysis with Ac2O-AcOH-H2SO4 solution were observed, with the beta-isomer giving acyclic sugar species together with the desired thiochitobiose peracetate 11, while the alpha-isomer gave exclusively the thiochitobiose peracetate 11. This remarkable difference between alpha- and beta-glycosides was further demonstrated by comparative acetolysis of methyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha- 23 and -beta-D-glucopyranoside 24. Methyl N,N',N ''-triacetylthiochitotriosides 29 and 30 were synthesized through conversion of N,N'-diacetylthiochitobiose peracetate 11 into N,N'-diacetyl-1,4-dithiochitobiose derivative 28, followed by its coupling with triflates 4 and 19 in the presence of cysteamine. Similarly, extension of the sugar chain to a higher homologue was achieved by converting methyl N,N',N ''-triacetylthiochitotrioside 30 into the N,N',N ''-triacetyl-1,4,4'-trithiochitotriose derivative 33, the coupling of which with triflate 19 in the presence of cysteamine provided the methyl N,N',N '',N triple prime-tetraacetylthiochitotetraoside 34 after de-O-acylation.