3,4,6-tri-O-benzoyl-2-(benzoyloximino)-2-deoxy-α-D-arabino-hexopyranosyl bromide | 82469-72-5

• 分子结构分类: 有机化合物
• 英文名称: 3,4,6-tri-O-benzoyl-2-(benzoyloximino)-2-deoxy-α-D-arabino-hexopyranosyl bromide
• 英文别名: tri-O-benzoyl-2-benzoyloxyimino-2-deoxy-α-D-arabinohexopyranosyl bromide；3,4,6-tri-O-benzoyl-2-benzoyloxyimino-α-D-arabino-hexopyranosyl bromide；3,4,6-tri-O-benzoyl-2-benzoyloximino-α-D-arabino-hexopyranosyl bromide；2-(benzoyloxyimino)glycosyl bromide
• CAS: 82469-72-5
• 化学式: C₃₄H₂₆BrNO₉
• 分子量: 672.486
• InChiKey: AZDIZBJORIBUSI-KLFPRNLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.63
• 重原子数：
  45.0
• 可旋转键数：
  9.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  126.79
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzoyl-2-(benzoyloximino)-2-deoxy-α-D-arabino-hexopyranosyl bromide 在 palladium on activated charcoal 硼烷四氢呋喃络合物 、 4 A molecular sieve 、 silver aluminosilicate 、 氢气 、 sodium methylate 、 溶剂黄146 作用下， 以 甲醇 、 水 为溶剂， -10.0~25.0 ℃ 、310.0 kPa 条件下， 反应 31.25h， 生成 3-O-(2-acetamido-2-deoxy-β-D-mannopyranosyl)-α-L-rhamnopyranose
  参考文献：
  名称：

  Syntheses of Three Interglycosidic Isomers of N-Acetyl-.BETA.-D-mannosaminyl-L-rhamnoses Associated with O-Antigens of Several Gram-Negative Opportunistic Pathogens.

  摘要：

  我们实现了N-乙酰基-β-D-甘露糖胺酰-L-鼠李糖三种糖苷间异构体的实用、高度立体选择性合成，其中β(1→4)异构体对应于机会性病原体铜绿假单胞菌O5和铜绿假单胞菌X（Meitert）的脂多糖（LPS）O抗原的重复单元。其他异构体是β(1→2)二糖（大肠杆菌O1A的LPS的成分）和人工β(1→3)异构体。二糖是通过简单的三步反应序列从2-(苯甲酰氧亚氨基)-2-脱氧糖基卤化物（甘露糖胺前体）获得的。对适当保护的L-鼠李糖基受体进行了β选择性糖基化。随后将2-酰氧亚氨基官能团还原为氨基，进行N-乙酰化，并去除保护基团，从而得到目标二糖。13C-NMR和核Overhauser效应谱被证明可用于确定二糖位置异构体的结构。

  DOI：

  10.1248/cpb.43.1441
• 作为产物：
  描述：

  1,5-anhydro-3,4,6-tri-O-benzoyl-D-fructose oxime 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 15.25h， 生成 3,4,6-tri-O-benzoyl-2-(benzoyloximino)-2-deoxy-α-D-arabino-hexopyranosyl bromide
  参考文献：
  名称：

  Lichtenthaler, Frieder W.; Jarglis, Pan; Hempe, Walter, Liebigs Annalen der Chemie, 1983, # 11, p. 1959 - 1972

  摘要：

  DOI：

文献信息

• A Practical Synthesis of Mannosaminyl-<i>β</i>(1→4)-glucosyl-<i>α</i>(1→2)-rhamnose, the Trisaccharide Repeating Unit of a<i>Streptococcus pneumoniae</i>Capsular Polysaccharide
  作者：Eisuke Kaji、Frieder W. Lichtenthaler、Yumiko Osa、Keiko Takahashi、Shonosuke Zen

  DOI：10.1246/bcsj.68.2401

  日期：1995.8

  An efficient chemical synthesis is described for the title trisaccharide repeating unit of the capsular polysaccharide of Streptococcus pneumoniae Type 19F. The key intermediate was a well-accessible indirect β-D-mannosaminyl donor, i.e. 2-(benzoyloxyimino)-2-deoxy-α-D-arabino-hexopyranosyl bromide, which underwent glycosidations with 20 : 1 β-selectivities; the benzoyloxyimino group was reduced with

  描述了一种有效的化学合成方法，用于 19F 型肺炎链球菌荚膜多糖的标题三糖重复单元。关键中间体是一种易于获得的间接 β-D-甘露糖胺基供体，即 2-(苯甲酰氧基亚氨基)-2-脱氧-α-D-阿拉伯-吡喃己糖基溴，其以 20:1 β-选择性进行糖苷化；苯甲酰氧基亚氨基以基本的甘露糖特异性被还原。以适当封闭形式获得的 ManNAc-β(1→4)-Glc 二糖随后被转化为 1-氟化物，L-鼠李糖受体通过 α(1→2) 键进行糖基化以产生目标D-葡萄糖所需的 13 个步骤的总产率为 6%。
• Practical Syntheses of Immunologically Relevant β-Glycosides of 2-Acetamido-2-deoxy-D-mannopyranose. Methyl<i>N</i>-Acetyl-β-D-mannosaminide,<i>N</i>-Acetyl-β-D-mannosaminyl-(1→6)-D-galactose, and Methyl<i>N</i>-Acetyl-β-D-mannosaminyl-(1→4)-α-D-glucopyranoside
  作者：Eisuke Kaji、Frieder W. Lichtenthaler、Takashi Nishino、Aya Yamane、Shonosuke Zen

  DOI：10.1246/bcsj.61.1291

  日期：1988.4

  Highly stereoselective, expedient syntheses are described for three immunologically relevant β-glycosides of N-acetyl-D-mannosamine, i.e. β-D-ManpNAc-1-OMe (8), β-D-ManpNAc-(1→6)-D-Gal (15), and β-D-ManpNAc-(1→4)-α-D-Glcp-1-OMe (23). Basic mannosamine progenitor in each case is 3,4,6-tri-O-benzoyl-2-(benzoyloxyimino)-2-deoxy-α-D-arabino-hexopyranosyl bromide (1a), which via the three step-sequence

  对 N-乙酰-D-甘露糖胺的三种免疫相关 β-糖苷，即 β-D-ManpNAc-1-OMe (8)、β-D-ManpNAc-(1→6)-D，描述了高度立体选择性、方便的合成-Gal (15) 和 β-D-ManpNAc-(1→4)-α-D-Glcp-1-OMe (23)。每种情况下的基本甘露糖胺前体是 3,4,6-tri-O-benzoyl-2-(benzoyloxyimino)-2-deoxy-α-D-arabino-hexopyranosyl bromide (1a)，它通过三个步骤序列 β-选择性糖苷化 → 硼氢化 → 去封闭转化为 8、15 和 23，糖基受体甲醇、1,2:3,4-二-O-异亚丙基-α-D-的总产率为 61%、56% 和 39%分别为半乳糖和甲基 2,3,6-三-O-苄基-α-D-吡喃葡萄糖苷。
• Various Glycosyl Donors with a Ketone or Oxime Function next to the Anomeric Centre: Facile Preparation and Evaluation of their Selectivities in Glycosidations
  作者：Frieder W. Lichtenthaler、Ulrich Kläres、Matthias Lergenmüller、Sabine Schwidetzky

  DOI：10.1055/s-1992-34167

  日期：——

  An efficient one-pot procedure is described for the conversion of a variety of hydroxyglycal esters to their 2-oxoglycosyl bromides which simply comprises of brief treatment with N-bromosuccinimide/methanol at ambient temperature. Exhibiting comparably low anomeric reactivity in glycosidation reactions, these ulosyl bromides, as well as their 2-benzoyloxyimino analogs, can readily be transformed into a range of more reactive glycosyl donors with iodine, pentenyloxy, ethylthio and dithiocarbamoyl residues at the anomeric centre, such that any ß-selective glycosidation may be successfullv achieved.

  描述了一种高效的一锅法步骤，用于将多种羟基甘油酯转化为其2-氧基糖苷溴化物，该过程仅涉及在室温下用N-溴琥珀酰亚胺/甲醇进行简短处理。这些氧基糖苷溴化物在糖苷化反应中表现出相对较低的异构体反应性，同时，它们的2-苯甲氧羰基亚氨基类似物也可以很容易地转化为一系列更具反应性的糖苷供体，这些供体在异构体中心具有碘、戊烯氧、乙硫基和二硫氨基甲酰基残基，从而可以成功实现任何β选择性的糖苷化反应。
• Radical-mediated bromination of carbohydrate derivatives: searching for alternative reaction conditions without carbon tetrachloride
  作者：Katalin Czifrák、László Somsák

  DOI：10.1016/s0040-4039(02)02205-0

  日期：2002.12

  KBrO3–Na2S2O4 in CH2Cl2–H2O or PhCF3–H2O biphasic solvent systems was applied to the bromination of several monosaccharide derivatives having capto-datively substituted reaction centres. With less reactive compounds neat PhCF3 was shown to be a suitable substitute of the health and environmentally hazardous carbon tetrachloride.

  在CH 2 Cl 2 -H 2 O或PhCF 3 -H 2 O双相溶剂体系中的KBrO 3 -Na 2 S 2 O 4被用于溴化具有巯基取代反应中心的几种单糖衍生物。活性较低的化合物表明，纯净的CFCF 3是健康和对环境有害的四氯化碳的合适替代品。
• An Alternative Access to a Trisaccharide Repeating Unit of the Capsular Polysaccharide of Streptococcus pneumoniae Serotype 19A.
  作者：Eisuke KAJI、Yumiko OSA、Mutsumi TANAIKE、Yugo HOSOKAWA、Hiroaki TAKAYANAGI、Atsushi TAKADA

  DOI：10.1248/cpb.44.437

  日期：——

  A chemical synthesis has been achieved for beta-D-ManNAc-(1-->4)-alpha-D-Glc-(1-->3)-L-Rha, a trisaccharide repeating unit of the capsular polysaccharide of Streptococcus pneumoniae serotype 19A, by stepwise link-up of the suitably functionalized, constituent sugar units. A beta-selective glycosylation of trimethylsilylethyl glucoside having free 4-OH with 2-(benzoyloxyimino)-2-deoxyglycosyl bromide

  化学合成已经实现了β-D-ManNAc-（1→4）-α-D-Glc-（1→3）-L-Rha，这是肺炎链球菌荚膜多糖的三糖重复单元。通过逐步连接适当官能化的糖单元，获得血清型19A。用2-（苯甲酰氧基亚氨基）-2-脱氧糖基溴化物将具有游离4-OH的三甲基甲硅烷基乙基葡糖苷进行β选择性糖基化，然后进行甘露聚糖选择性硼氢化，N-乙酰化和异头中心官能化（1-OSE-> 1 -OH-> 1-F），得到关键的二糖供体，β-D-ManNAc-（1-> 4）-alpha-D-Glc-（1-> F.L-鼠李糖基糖基化解封后，具有供体底物的受体受体在13步中从D-葡萄糖以6.5％的产率提供了目标三糖。