thioethyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside | 1043887-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: thioethyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside
• CAS: 1043887-05-3
• 化学式: C₁₇H₂₁N₃O₅S
• 分子量: 379.437
• InChiKey: YRPIOHOHUBZWBU-HDKMNVHJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.19
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  102.75
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  thioethyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 2,6-二甲基吡啶 、 三氟甲磺酸二丁硼 、 硼烷 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以2.04 g的产率得到
  参考文献：
  名称：

  Solid-Phase Synthesis of α-Glucosamine Sulfoforms with Fragmentation Analysis by Tandem Mass Spectrometry

  摘要：

  Sulfated epitopes of alpha-glucosamine (GlcN sulfoforms) were prepared by solid-phase synthesis as models of internal glucosamines within heparan sulfate. An orthogonally protected 2'-hydroxyethyl GlcN derivative was immobilized on a trityl resin support and subjected to regioselective deprotection and sulfonation conditions, which were optimized with the aid of on-resin infrared or Raman analysis. The sulfoforms were cleaved from the resin under mild Lewis acid conditions without affecting the O- or N-sulfate groups and purified by reversed-phase high-performance liquid chromatography (HPLC). The alpha-GlcN sulfoforms and their 4-O-benzyl ethers were examined by electrospray ionization tandem mass spectrometry (ESI-MS/MS), with product ion spectra produced by collision-induced dissociation (CID). ESI-MS/MS revealed significant differences in parent ion stabilities and fragmentation rates as a function of sulfate position. Ion fragmentation by CID resulted in characteristic mass losses with strong correlation to the positions of both free hydroxyl groups and sulfate ions. Most of these fragmentation patterns are consonant with elimination pathways, and suggest possible strategies for elucidating the structures of glucosamine-derived sulfoforms with identical m/z ratios. In particular, fragmentation analysis can easily distinguish GlcN sulfoforms bearing the relatively rare 3-O-sulfate from isomers with the more common 6-O-sulfate.

  DOI：

  10.1021/jo800713m
• 作为产物：
  描述：

  、 乙酸酐 在 吡啶 作用下， 反应 10.0h， 以6.6 g的产率得到thioethyl 3-O-acetyl-2-azido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Solid-Phase Synthesis of α-Glucosamine Sulfoforms with Fragmentation Analysis by Tandem Mass Spectrometry

  摘要：

  Sulfated epitopes of alpha-glucosamine (GlcN sulfoforms) were prepared by solid-phase synthesis as models of internal glucosamines within heparan sulfate. An orthogonally protected 2'-hydroxyethyl GlcN derivative was immobilized on a trityl resin support and subjected to regioselective deprotection and sulfonation conditions, which were optimized with the aid of on-resin infrared or Raman analysis. The sulfoforms were cleaved from the resin under mild Lewis acid conditions without affecting the O- or N-sulfate groups and purified by reversed-phase high-performance liquid chromatography (HPLC). The alpha-GlcN sulfoforms and their 4-O-benzyl ethers were examined by electrospray ionization tandem mass spectrometry (ESI-MS/MS), with product ion spectra produced by collision-induced dissociation (CID). ESI-MS/MS revealed significant differences in parent ion stabilities and fragmentation rates as a function of sulfate position. Ion fragmentation by CID resulted in characteristic mass losses with strong correlation to the positions of both free hydroxyl groups and sulfate ions. Most of these fragmentation patterns are consonant with elimination pathways, and suggest possible strategies for elucidating the structures of glucosamine-derived sulfoforms with identical m/z ratios. In particular, fragmentation analysis can easily distinguish GlcN sulfoforms bearing the relatively rare 3-O-sulfate from isomers with the more common 6-O-sulfate.

  DOI：

  10.1021/jo800713m

文献信息

• Expeditious Synthesis of the Hexasaccharide Repeating Unit of the Capsular Polysaccharide of Streptococcus pneumoniae Type 7A
  作者：Samim Sahaji、Pradip Shit、Anup Kumar Misra、Swapan Kumar Jana

  DOI：10.1055/s-0040-1720095

  日期：2024.4

  The hexasaccharide repeating unit corresponding to the capsular polysaccharide of Streptococcus pneumoniae type 7A has been synthesized in good yield using [3+2+1] block synthetic strategy. The synthetic strategy involved a number of challenging stereoselective glycosylation steps, which include β-selective glycosylation of l-rhamnosyl thioglycoside donor, α-selective glycosylations of 2-azido-2-d

  采用[3+2+1]嵌段合成策略，以良好的产率合成了与7A型肺炎链球菌荚膜多糖相对应的六糖重复单元。该合成策略涉及许多具有挑战性的立体选择性糖基化步骤，其中包括我-鼠李糖基硫代糖苷供体，2-叠氮基-2-脱氧-的α-选择性糖基化-d-吡喃葡萄糖基硫代糖苷供体和d-吡喃半乳糖基供体与β-糖苷的形成d-半乳糖胺部分和α-糖苷我-鼠李糖基部分。适当官能化的硫代糖苷已被用作糖基供体，并且N-碘代琥珀酰亚胺(NIS)和三甲基甲硅烷基三氟甲磺酸酯(TMSOTf)的组合已被用作糖基化促进剂。