3,4,6-tri-O-benzyl-1,2-O-(α-methoxybenzylidene)-β-D-mannopyranose | 915150-03-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4,6-tri-O-benzyl-1,2-O-(α-methoxybenzylidene)-β-D-mannopyranose
• 英文别名: 1,2-O-(methoxyphenylmethylene)-3,4,6-tri-O-benzyl-D-mannopyranose；1,2-O-(methoxyphenylmethylene)-3,4,6-tri-O-benzyl-β-D-mannopyranoside；methyl 3,4,6-tri-O-benzyl mannopyranosyl 1,2-orthobenzoate；(3aS,5R,6R,7S,7aS)-2-methoxy-2-phenyl-6,7-bis(phenylmethoxy)-5-(phenylmethoxymethyl)-5,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-b]pyran
• CAS: 915150-03-7
• 化学式: C₃₅H₃₆O₇
• 分子量: 568.667
• InChiKey: KEBHBXQORQYOIO-AGLPCPFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  42
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-1,2-O-(α-methoxybenzylidene)-β-D-mannopyranose 在 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.75h， 生成 1-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-α-D-mannopyranosyl) trichloroacetimidate
  参考文献：
  名称：

  Synthesis of a Core Arabinomannan Oligosaccharide of Mycobacterium tuberculosis

  摘要：

  The synthesis of a core arabinomannan (AM) oligosaccharide from Mycobacterium tuberculosis has been achieved using a convergent [6 + 6] glycosylation strategy and a defined set of building blocks. Dodecasaccharide 1, containing the key AM structural features of lipoarabinomannan (LAM), was obtained in excellent yield and selectivity from hexamannan 3 and hexaarabinan 5. This flexible synthetic strategy involves late-stage couplings and modifications, thus providing ready access to several different LAM fragments. The incorporation of a thiol linker at the reducing end of the oligosaccharide allows for the attachment of these compounds to microarrays and protein carriers.

  DOI：

  10.1021/jo061233x
• 作为产物：
  描述：

  1,2-O-(α-methoxybenzylidene)-3,4,6-tri-O-benzoyl-β-D-mannopyranose 在 咪唑 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.5h， 生成 3,4,6-tri-O-benzyl-1,2-O-(α-methoxybenzylidene)-β-D-mannopyranose
  参考文献：
  名称：

  Synthesis of a Core Arabinomannan Oligosaccharide of Mycobacterium tuberculosis

  摘要：

  The synthesis of a core arabinomannan (AM) oligosaccharide from Mycobacterium tuberculosis has been achieved using a convergent [6 + 6] glycosylation strategy and a defined set of building blocks. Dodecasaccharide 1, containing the key AM structural features of lipoarabinomannan (LAM), was obtained in excellent yield and selectivity from hexamannan 3 and hexaarabinan 5. This flexible synthetic strategy involves late-stage couplings and modifications, thus providing ready access to several different LAM fragments. The incorporation of a thiol linker at the reducing end of the oligosaccharide allows for the attachment of these compounds to microarrays and protein carriers.

  DOI：

  10.1021/jo061233x

文献信息

• Expedient synthesis of the heneicosasaccharyl mannose capped arabinomannan of the Mycobacterium tuberculosis cellular envelope by glycosyl carbonate donors
  作者：Maidul Islam、Ganesh P. Shinde、Srinivas Hotha

  DOI：10.1039/c6sc04866h

  日期：——

  The global incidence of tuberculosis is increasing at an alarming rate, and Mycobacterium tuberculosis (Mtb) is the causative agent for tuberculosis, a disease with high mortality. Lipoarabinomannan (LAM) is one of the major components of the Mtb cellular envelope and is an attractive scaffold for developing anti-tubercular drugs, vaccines and diagnostics. Herein, a highly convergent strategy is developed

  结核病的全球发病率正以惊人的速度增长，结核分枝杆菌（Mtb）是导致高死亡率的结核病的病原体。Lipoarabinomannan（LAM）是Mtb细胞包膜的主要成分之一，是开发抗结核药，疫苗和诊断剂的有吸引力的支架。本文中，首次提出了高度收敛的策略以合成heneicosasaccharyl arabinomannan。在这项工作中所合成的arabinomannan具有几个1,2-反式或α-阿糖胞苷˚F键和三个1,2-顺或β-阿糖胞苷˚F键端与封端的1,2-反式或α-曼p联系。所有关键的糖苷化反应都是在[Au] / [Ag]催化条件下用碳酸炔基糖基供体进行的，即使对于复杂的和支链的低聚糖之间的反应，也具有出色的收率和立体选择性。将所得的烯丙基寡糖整体脱保护，以得到半纤维素糖基阿拉伯甘露聚糖，其为丙基糖苷。总之，用56个步骤完成了heneicosasaccharyl甘露糖加帽的阿拉伯甘露聚糖的合成，总收率为0
• A Concise Synthesis of a BODIPY-Labeled Tetrasaccharide Related to the Antitumor PI-88
  作者：Juan Ventura、Clara Uriel、Ana M. Gomez、Edurne Avellanal-Zaballa、Jorge Bañuelos、Inmaculada García-Moreno、Jose Cristobal Lopez

  DOI：10.3390/molecules26102909

  日期：——

  A convergent synthetic route to a tetrasaccharide related to PI-88, which allows the incorporation of a fluorescent BODIPY-label at the reducing-end, has been developed. The strategy, which features the use of 1,2-methyl orthoesters (MeOEs) as glycosyl donors, illustrates the usefulness of suitably-designed BODIPY dyes as glycosyl labels in synthetic strategies towards fluorescently-tagged oligosaccharides

  已经开发出一种与 PI-88 相关的四糖的聚合合成路线，该路线允许在还原端掺入荧光 BODIPY 标记。该策略的特点是使用 1,2-甲基原酸酯 (MeOE) 作为糖基供体，说明了适当设计的 BODIPY 染料作为糖基标记在荧光标记寡糖的合成策略中的有用性。
• BODIPYs as Chemically Stable Fluorescent Tags for Synthetic Glycosylation Strategies towards Fluorescently Labeled Saccharides
  作者：Clara Uriel、Caterina Permingeat、Juan Ventura、Edurne Avellanal‐Zaballa、Jorge Bañuelos、Inmaculada García‐Moreno、Ana M. Gómez、J. Cristobal Lopez

  DOI：10.1002/chem.201905780

  日期：2020.4.24

  chromophores on the ensuing compounds grants access to fluorescently labeled saccharides. In this context, a sought-after feature of the fluorescent dyes has been their chemical robustness. Accordingly, some BODIPY derivatives described in this work can withstand the reaction conditions commonly employed in the chemical synthesis of saccharides; namely, glycosylation and protecting-group manipulations. Regarding

  已经设计了一系列荧光硼-二吡咯亚甲基（BODIPY，4,4-二氟-4-硼3a，4a-二氮杂-s-茚并四烯）染料作为糖苷配基参与合成的寡糖方案。因此，它们具有双重目的：首先，通过在过程开始时（在生长的糖部分的还原端）掺入，它们可以充当荧光糖基标签，从而促进所需糖苷的检测和纯化。中间体，其次，这些发色团在随后的化合物上的存在允许获得荧光标记的糖类。在这种情况下，荧光染料的抢手特征是其化学稳定性。因此，这项工作中描述的某些BODIPY衍生物可以承受糖类化学合成中通常使用的反应条件。即糖基化和保护基操纵。关于它们的光物理性质，在这项工作中获得的BODIPY标记的糖类在水中显示出显着的荧光效率，达到高达82％的量子产率值，并且具有显着的激光效率和光稳定性。
• Glycosyl Formates: Glycosylations with Neighboring-Group Participation
  作者：Liang Yang、Christian Marcus Pedersen

  DOI：10.3390/molecules27196244

  日期：——

  model glycosyl acceptors of varied steric bulk and reactivity. Bismuth triflate was the preferred catalyst and KPF6 was used as an additive. The 1,2-trans-selectivities resulting from neighboring-group participation were excellent and the glycosylations were generally high-yielding.

  使用甲酸作为唯一试剂，由相应的原酸酯一步合成受保护的 2-O-苄基化糖基甲酸酯。合成了吡喃葡萄糖基、吡喃甘露糖基和吡喃半乳糖基供体，并使用具有不同空间体积和反应性的模型糖基受体研究了它们的糖基化特性。三氟甲磺酸铋是优选的催化剂，KPF 6用作添加剂。由相邻组参与产生的 1,2-反式选择性非常好，并且糖基化通常是高产的。
• Tf2O/TfOH catalytic glycosylation using o-(p-methoxyphenylethynyl)benzyl glycosides as donors and its application in synthesis of oligosaccharides
  作者：Xinguang Lan、Chenglin Cai、Jincai Wang、Qi Zhang、Yingle Feng、Yonghai Chai

  DOI：10.1016/j.tetlet.2023.154342

  日期：2023.2

  A catalytic glycosylation protocol was established using Tf2O or TfOH as catalyst and o-(p-methoxyphenylethynyl)benzyl (MPEB) glycosides as donors. The MPEB donors are stable and readily prepared from inexpensive starting material. The donors were activated by 10 mol% Tf2O or TfOH and coupled with various acceptors to provide desired glycosides in modest to good yield. This glycosylation protocol was

  使用 Tf 2 O 或 TfOH 作为催化剂并使用o -(对甲氧基苯基乙炔基) 苄基 (MPEB) 糖苷作为供体建立催化糖基化方案。MPEB 供体稳定且易于从廉价的起始材料制备。供体被 10 mol% Tf 2 O 或 TfOH 激活，并与各种受体偶联，以适度到良好的产率提供所需的糖苷。该糖基化方案通过“潜在活性”策略进一步应用于线性六甘露糖的合成。