methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-trifluormethanesulfonyl-β-D-galactopyranoside | 176690-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-trifluormethanesulfonyl-β-D-galactopyranoside
• 英文别名: Bz(-3)[Tf(-4)][Bz(-6)]b-GalNAc1Me；[(2R,3R,4R,5R,6R)-5-acetamido-4-benzoyloxy-6-methoxy-3-(trifluoromethylsulfonyloxy)oxan-2-yl]methyl benzoate
• CAS: 176690-92-9
• 化学式: C₂₄H₂₄F₃NO₁₀S
• 分子量: 575.516
• InChiKey: VESCRFBSIRVGRO-DUXQTRJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  152
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-trifluormethanesulfonyl-β-D-galactopyranoside 在 氢氧化钾 、 二乙胺基三氟化硫 、 sodium nitrite 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.5h， 生成 methyl 2-acetamido-2,4-dideoxy-4-fluoro-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of 4-deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-d-glucose and 2-acetamido-2-deoxy-d-galactose and their effects on cellular glycosaminoglycan biosynthesis

  摘要：

  4-Deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-D-glucose and 2-acetamido-2-deoxy-D-galactose were synthesized and evaluated as inhibitors of hepatic glycosaminoglycan biosynthesis. 2-Acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-glucopyranose (16) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation into hepatocyte cellular glycosaminoglycans to 12 and 18%, respectively, of the control cells, at 1.0 mM. Similarly, 2-acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-gala (31) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation to 1 and 9%. respectively, of the control cells, at 1.0 mM. Unlike 16, 31 exhibited a reduction of [C-14]Leu incorporation into cellular protein to 57% of control cells, at 1.0 mM. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(00)00049-5
• 作为产物：
  描述：

  2-乙酰氨基-3,4,6-三-O-乙酰-2-脱氧-α-D-吡喃葡萄糖酰基氯 在 吡啶 、 sodium methylate 、 sodium nitrite 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 21.5h， 生成 methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-trifluormethanesulfonyl-β-D-galactopyranoside
  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.
• Synthesis of 4-deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-d-glucose and 2-acetamido-2-deoxy-d-galactose and their effects on cellular glycosaminoglycan biosynthesis
  作者：Ali Berkin、Walter A. Szarek*、Robert Kisilevsky*

  DOI：10.1016/s0008-6215(00)00049-5

  日期：2000.6

  4-Deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-D-glucose and 2-acetamido-2-deoxy-D-galactose were synthesized and evaluated as inhibitors of hepatic glycosaminoglycan biosynthesis. 2-Acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-glucopyranose (16) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation into hepatocyte cellular glycosaminoglycans to 12 and 18%, respectively, of the control cells, at 1.0 mM. Similarly, 2-acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-gala (31) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation to 1 and 9%. respectively, of the control cells, at 1.0 mM. Unlike 16, 31 exhibited a reduction of [C-14]Leu incorporation into cellular protein to 57% of control cells, at 1.0 mM. (C) 2000 Elsevier Science Ltd. All rights reserved.