6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl chloride | 4356-78-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl chloride
• 英文别名: [(2R,3R,4S,5R,6R)-6-chloro-3,4,5-tris(phenylmethoxy)oxan-2-yl]methyl acetate
• CAS: 4356-78-9
• 化学式: C₂₉H₃₁ClO₆
• 分子量: 511.015
• InChiKey: WOLMTVURXQGEOM-RQKPWJHBSA-N

物化性质

• 熔点：
  63-64 °C(Solv: ligroine (8032-32-4))
• 沸点：
  611.0±55.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl chloride 在 N-碘代丁二酰亚胺 、 molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 0.67h， 生成 benzyl (6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl)-(1->3)-(2,4-di-O-benzyl-α-L-rhamnopyranosyl)-(1->2)-3,4-di-O-benzyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of the α-d-GlcpA-(1→3)-α-l-Rhap-(1→2)-l-Rha trisaccharide isolated from the cell wall hydrolyzate of the green alga, Chlorella vulgaris

  摘要：

  The title trisaccharide was synthesized from 6-O-acetyl-2,3,4-tri-O-benzyl-alpha -D-glucopyranosyl chloride (10), ethyl 2,4-di-O-benzyl-1-thio- (5) and benzyl 3,4-di-O-benzyl-alpha -L-rhamnopyranoside (9). The disaccharide 11 obtained from compounds 5 and 10 was used as the glycosyl donor to glycosylate the rhamnopyranoside derivative 9 having free OH-2 using the NIS-AgOTf-mediated glycosylation methodology. Zemplen deacetylation of the trisaccharide 12 resulted in the 6 " -OH derivative (13), which was selectively oxidized with CrO3 to the uronic acid derivative 14. The benzyl groups were removed by catalytic hydrogenolysis to furnish the target trisaccharide (1). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00196-3
• 作为产物：
  描述：

  6-O-acetyl-2,3,4-tri-O-benzyl-D-glucopyranose 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 反应 2.0h， 以89%的产率得到6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl chloride
  参考文献：
  名称：

  [EN] STABLE VACCINE AGAINST CLOSTRIDIUM DIFFICILE
  [FR] VACCIN STABLE DIRIGÉ CONTRE CLOSTRIDIUM DIFFICILE

  摘要：

  本发明涉及一种与Clostridium difficile PS-II细胞表面多糖及其共轭物相关的通用式(I)的合成糖苷。所述合成糖苷，所述共轭物以及含有所述合成糖苷或所述共轭物的药物组合物对于预防和/或治疗与Clostridium difficile相关的疾病是有用的。此外，通用式(I)的合成糖苷在免疫学检测中作为标记物是有用的，用于检测针对Clostridium difficile细菌的抗体。

  公开号：

  WO2020104697A1

文献信息

• Systematic chemical synthesis and n.m.r. spectra of methyl α-glycosides of isomalto-oligosaccharides and related compounds
  作者：Pavol Kováč、Laura Lerner

  DOI：10.1016/0008-6215(88)80008-9

  日期：1988.12

  nucleophile, and silver perchlorate as the promoter. The n.m.r. spectra (1H- and 13C-) of numerous 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 beta-glycosyl

  1,6-脱水-2,3,4-三-O-苄基-β-D-吡喃葡萄糖的酸催化硫酚氧化反应和所得苯基2,3,4-三-O-苄基-1-硫代-苯甲酸乙酰化α-D-吡喃葡萄糖苷（4）得到苯基6-O-乙酰基-2,3,4-三-O-苄基-1-硫代-α-D-吡喃葡萄糖苷（5）。5与氯的反应立体定向产生相应的β-糖基氯，将其在高氯酸银和2,4,6-三甲基吡啶的存在下用4处理，得到苯基O-（6-O-乙酰基-2,3 ，4-三-O-苄基-α-D-吡喃葡萄糖基）-（1-6）-2,3,4-三-O-苄基-1-硫代-α-D-吡喃葡萄糖苷（17）。结晶O-（6-O-乙酰基-2,3,4-三-O-苄基-α-D-吡喃葡萄糖基）-（1 ---- 6）-2,3,4-三-O-苄基- β-D-吡喃葡萄糖基氯，可以通过用氯处理以立体特异性的方式容易地从17中获得，在异麦芽寡糖，直至并包括八糖的甲基糖苷的嵌段合成中，“苯丙氨酸”用作关键糖基（异麦芽糖基）供体。通过使用SnCl2活化的2
• Inhibitors of <i>endo</i>-α-mannosidase. Part III. Congeners of 1-deoxy-3-<i>O</i>-(α-<scp>D</scp>-glucopyranosyl)-mannojirimycin modified in the glucose unit
  作者：Ulrike Spohr、Mimi Bach

  DOI：10.1139/v93-241

  日期：1993.11.1

  The syntheses of congeners of 1-deoxy-3-O-(α-D-glucopyranosyl)-mannojirimycin (1), a strong inhibitor of the glycoprotein-processing endo-mannosidase, are described. The chemical modifications of 1 involved all monodeoxy-genations and mono-O-methylations of the glucose unit and the replacement of this unit by D-galactose, D-xylose, and 2-chloro-2-deoxy-D-glucose. As reported previously, none of the modifications of 1, including deoxygenations and O- and N-methylations of the deoxymannojirimycin unit, improved the inhibitory properties, but demonstrated the high specificity in the recognition of 1 by the enzyme and allowed the assignment of intermolecular hydrogen bonds of the inhibitor • enzyme complex. Essential for complex formation were found NH-5, OH-2, OH-4, and OH-6 of the DMJ unit, as well as OH-3′, OH-4′, and CH₂-6′ of the glucose unit. The residual activities on deoxygenating the OH-2′ and OH-6′ groups of 1 suggest their involvement at the periphery of the binding site.

  描述了一种强烈抑制糖蛋白处理内切脱甲基酶的1-去氧-3-O-(α-D-葡萄糖吡喃基)-曼诺基霉素（1）同系物的合成。1的化学改性包括所有单去氧基化和单-O-甲基化葡萄糖单元以及将该单元替换为D-半乳糖、D-木糖和2-氯-2-脱氧-D-葡萄糖。正如先前报道的那样，1的所有改性，包括去氧化和去氧曼诺基霉素单元的O-和N-甲基化，都没有改善抑制性能，但表明了对酶识别1的高特异性，并允许分配抑制剂•酶复合物的分子间氢键。复合物形成所需的关键部位包括DMJ单元的NH-5、OH-2、OH-4和OH-6，以及葡萄糖单元的OH-3′、OH-4′和CH2-6′。对于1的OH-2′和OH-6′基团的去氧化残余活性表明它们参与了结合位点的外围。
• Synthesis of methyl 6″-deoxy-6′-fluoro-α-isomaltoside and of the corresponding trisaccharide
  作者：Pavol Kováč、Vladimír Sklenář、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(88)84143-0

  日期：1988.5

  6-trimethylpyridine. O-Deacetylation of 5 , followed by treatment of the formed 6 , containing only HO-6′ unsubstituted, with diethylaminosulfur trifluoride (DAST) or dimethylaminosulfur trifluoride (methyl DAST) gave the per- O -benzyl derivative ( 9 ) of methyl 6′-deoxy-6′-fluoro-α-isomaltoside. Compound 9 was also obtained by condensation of 1 with 2,3,4-tri- O -benzyl-6-deoxy-6-fluoro-β- d -glucopyranosyl fluoride

  摘要甲基6-O-（6-O-乙酰基-2,3,4-三-O-苄基-α-d-吡喃葡萄糖基）-2,3,4-三-O-苄基-α-d-吡喃葡萄糖苷（当2,3,4-三-O-苄基-α-d-吡喃葡萄糖基（1）与6-O-乙酰基-2,3,4-三-O-苄基缩合时，形成具有高立体选择性的5）在2,4,6-三甲基吡啶存在下，用高氯酸银促进乙醚中的-α-d-吡喃葡萄糖基氯。5的O-脱乙酰化，然后用二乙基氨基三氟化硫（DAST）或二甲基氨基三氟化硫（甲基DAST）处理仅含未取代的HO-6'的生成的6，得到甲基6'的全-O-苄基衍生物（9） -脱氧-6'-氟-α-异麦芽糖苷。还可以通过1与2,3的缩合反应获得化合物9，在高氯酸银和无水氯化亚锡存在下的4-三-O-苄基-6-脱氧-6-氟-β-d-吡喃葡萄糖基氟（4）。通过将6与4缩合获得6-脱氧-6-氟-异麦芽三糖的完全苄基化的甲基α-糖苷（15）。9和15 gae的氢解异麦芽糖
• Conversion of p-methoxyphenyl glycosides into the corresponding glycosyl chlorides and bromides, and into thiophenyl glycosides
  作者：Zhiyuan Zhang、Göran Magnusson

  DOI：10.1016/s0008-6215(96)90118-4

  日期：1996.12

  Treatment of the pMP glycosides with acyl chlorides or bromides in the presence of various Lewis acids gave the corresponding glycosyl chlorides and bromides in 81-98% yield. Treatment of the acyl-protected pMP glycosides with thiophenol and boron trifluoride etherate gave the corresponding thioglycosides in 80-100% yield and high (> 20:1) beta/alpha selectivity. The stability of pMP glycosides was investigated

  使用硼从相应的1-O-乙酰基糖中制备对甲氧基苯基（pMP）β-D-吡喃葡萄糖苷（Glc，Gal，GlcNPhth，GalNPhth，GlcNTroc，Gal beta 4Glc，Gal alpha 4Gal），使用硼制得三氟化醚醚为助催化剂。在各种路易斯酸的存在下用酰氯或溴化物处理pMP糖苷得到相应的糖酰氯和溴化物，产率为81-98％。用硫酚和三氟化硼醚化物处理酰基保护的pMP糖苷，可以80-100％的收率和高（> 20：1）β/ alpha选择性获得相应的硫糖苷。针对一系列试剂研究了pMP糖苷的稳定性。
• Synthesis of methyl glycosides of some α-isomalto oligosaccharides specifically deoxygenated at position C-2
  作者：Eva Petráková、Cornelis P.J. Glaudemans

  DOI：10.1016/0008-6215(94)00314-6

  日期：1995.3

  Methyl alpha-isomaltoside and methyl alpha-isomaltotrioside analogues specifically deoxygenated at position C-2 of various glucopyranosyl units were synthesized by condensation of either 6-O-acetyl-3-O-benzoyl-4-O-benzyl-1-O-tert-butyldimethylsilyl-2-deoxy- beta-D-arabino-hexopyranose (trimethylsilyl triflate mediated) or 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl chloride (mediated by silver

  通过6-O-乙酰基-3-O-苯甲酰基-4-O-苄基-1-O-叔胺的缩合反应合成了在各种吡喃葡萄糖基单元的C-2位特别脱氧的甲基α-异麦芽糖苷和甲基α-异麦芽糖苷类似物-丁基二甲基甲硅烷基-2-脱氧-β-D-阿拉伯糖基六氢吡喃糖（三氟甲磺酸三甲基甲硅烷基酯介导）或6-O-乙酰基-2,3,4-三-O-苄基-α-D-吡喃葡萄糖基氯（由碳酸银和（三氟甲磺酸银）与甲基α-D-吡喃葡萄糖苷，其2-脱氧类似物或甲基2'-脱氧-α-异麦芽糖苷的适当嵌段的衍生物。