thioethyl 3,4,6-tri-O-benzyl-2-O-pivaloyl-β-D-mannopyranoside | 196704-20-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: thioethyl 3,4,6-tri-O-benzyl-2-O-pivaloyl-β-D-mannopyranoside
• 英文别名: pivaloyl(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Man(b)-SEt；[(2S,3S,4S,5R,6R)-2-ethylsulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] 2,2-dimethylpropanoate
• CAS: 196704-20-8
• 化学式: C₃₄H₄₂O₆S
• 分子量: 578.77
• InChiKey: UMQPBJUBZWFXNM-KQLGDFJMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  41
• 可旋转键数：
  15
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  88.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-O-p-methoxybenzyl-D-glucal 、 thioethyl 3,4,6-tri-O-benzyl-2-O-pivaloyl-β-D-mannopyranoside 在 二叔丁基过氧化物 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 为溶剂， 以63%的产率得到[(2S,3S,4S,5R,6R)-2-[[(2R,3S,4R)-4-[(2S,3S,4S,5R,6R)-3-(2,2-dimethylpropanoyloxy)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxy-3-[(4-methoxyphenyl)methoxy]-3,4-dihydro-2H-pyran-2-yl]methoxy]-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] 2,2-dimethylpropanoate
  参考文献：
  名称：

  A Highly Convergent Total Synthetic Route to Glycopeptides Carrying a High-Mannose Core Pentasaccharide DomainN-linked to a Natural Peptide Motif

  摘要：

  AbstractN‐Linked glycopeptides were synthesized by condensation of a highmannose anomeric amine bearing a pentasaccharide with aspartic‐acid‐containing tri‐ and pentapeptides through the agency of IIDQ. The pentasaccharide portion, corresponding to the „core”︁ region of all asparagine‐linked glycoproteins, was assembled by means of glycal‐derived thioethyl donors and glycal acceptors. The central mannose residue was established by inversion of the C2 hydroxyl of a glucosyl precursor in the pentasaccharide. The protecting‐group scheme employed allows the extension of the pentasaccharide through the terminal mannose units. While a fully convergent coupling of the high‐mannose carbohydrate to the peptide domain has thus been accomplished for the first time with a fully synthetic sugar, the stereochemical integrity of the anomeric center of the carbohydrate domain was not maintained and a mixture of glycopeptides was obtained.

  DOI：

  10.1002/chem.19970031011
• 作为产物：
  描述：

  ethyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 乙酸酐 、 二甲基亚砜 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 thioethyl 3,4,6-tri-O-benzyl-2-O-pivaloyl-β-D-mannopyranoside
  参考文献：
  名称：

  糖基衍生的硫乙基糖基供体与糖基受体的偶联。糖醛组装范围的进展

  摘要：

  糖醛通过 1,2-脱水糖中间体转化为硫乙基糖基供体。检查了 C-2 位置的各种参与基团的 β-葡萄糖基、β-半乳糖基和 α-甘露糖基键的形成。使用涉及硫乙基 2-新戊酰基糖基供体和糖受体的新型偶联方案制备了许多二糖。使用这种方法，以高产率制备了仅含有 β-葡萄糖基-(1→4) 键的线性四糖。α-甘露糖基化和 C2 分支的现成应用是该方法的其他标志。

  DOI：

  10.1021/ja971640d

文献信息

• Solution and Solid-Support Synthesis of a Potential Leishmaniasis Carbohydrate Vaccine
  作者：Michael C. Hewitt、Peter H. Seeberger

  DOI：10.1021/jo015521z

  日期：2001.6.1

  The synthesis of a potential carbohydrate vaccine for the parasitic disease leishmaniasis is described. New solution- and solid-phase synthetic strategies were explored for the assembly of a unique tetrasaccharide antigen found on the Leishmania lipophosphoglycan. An initial solution-phase synthesis relied on thioglycosides as building blocks and the establishment of the central disaccharide from lactal

  描述了用于寄生虫利什曼病的潜在碳水化合物疫苗的合成。探索了新的溶液和固相合成策略，用于组装在利什曼原虫脂磷酸聚糖上发现的独特的四糖抗原。最初的溶液相合成依赖于硫糖苷作为结构单元，并通过氧化还原序列从乳清中建立了中心二糖。在解决方案和固体支持上都完成了第二种方法。固相合成依赖于单糖单元的组装，并用于评估有效安装半乳糖β-（1-4）甘露糖苷中的不同糖基化剂。事实证明，糖基磷酸酯最成功。利什曼原虫菌盖的第一次固相合成提供了以18％的总收率快速获得四糖的途径，而仅需一个纯化步骤。将合成的帽四糖与免疫刺激剂Pam3Cys结合以生成完全合成的碳水化合物疫苗1，并与载体蛋白KLH结合以形成半合成疫苗2。目前，这两种构建体均已在小鼠体内进行了初步免疫学实验，旨在开发针对寄生虫的疫苗疾病利什曼病。
• A Highly Convergent Total Synthetic Route to Glycopeptides Carrying a High-Mannose Core Pentasaccharide DomainN-linked to a Natural Peptide Motif
  作者：Samuel J. Danishefsky、Shuanghua Hu、Pier F. Cirillo、Matthias Eckhardt、Peter H. Seeberger

  DOI：10.1002/chem.19970031011

  日期：1997.10

  AbstractN‐Linked glycopeptides were synthesized by condensation of a highmannose anomeric amine bearing a pentasaccharide with aspartic‐acid‐containing tri‐ and pentapeptides through the agency of IIDQ. The pentasaccharide portion, corresponding to the „core”︁ region of all asparagine‐linked glycoproteins, was assembled by means of glycal‐derived thioethyl donors and glycal acceptors. The central mannose residue was established by inversion of the C2 hydroxyl of a glucosyl precursor in the pentasaccharide. The protecting‐group scheme employed allows the extension of the pentasaccharide through the terminal mannose units. While a fully convergent coupling of the high‐mannose carbohydrate to the peptide domain has thus been accomplished for the first time with a fully synthetic sugar, the stereochemical integrity of the anomeric center of the carbohydrate domain was not maintained and a mixture of glycopeptides was obtained.
• Coupling of Glycal Derived Thioethyl Glycosyl Donors with Glycal Acceptors. An Advance in the Scope of the Glycal Assembly
  作者：Peter H. Seeberger、Matthias Eckhardt、Clare E. Gutteridge、Samuel J. Danishefsky

  DOI：10.1021/ja971640d

  日期：1997.10.1

  Glycals were converted into thioethyl glycosyl donors through 1,2-anhydrosugar intermediates. Various participating groups in the C-2 position were examined for formation of β-glucosyl, β-galactosyl, and α-mannosyl linkages. A number of disaccharides was prepared employing a novel coupling protocol involving thioethyl 2-pivaloyl glycosyl donors and glycal acceptors. Using this methodology, a linear

  糖醛通过 1,2-脱水糖中间体转化为硫乙基糖基供体。检查了 C-2 位置的各种参与基团的 β-葡萄糖基、β-半乳糖基和 α-甘露糖基键的形成。使用涉及硫乙基 2-新戊酰基糖基供体和糖受体的新型偶联方案制备了许多二糖。使用这种方法，以高产率制备了仅含有 β-葡萄糖基-(1→4) 键的线性四糖。α-甘露糖基化和 C2 分支的现成应用是该方法的其他标志。