triphenylmethyl 1-thio-α-D-mannopyranoside | 616238-31-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: triphenylmethyl 1-thio-α-D-mannopyranoside
• 英文别名: (2R,3S,4S,5S,6R)-2-(hydroxymethyl)-6-tritylsulfanyloxane-3,4,5-triol
• CAS: 616238-31-4
• 化学式: C₂₅H₂₆O₅S
• 分子量: 438.544
• InChiKey: UBPCIWQPGUEYSM-URYYLNOGSA-N

物化性质

• 沸点：
  630.2±55.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  31
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  115
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  triphenylmethyl 1-thio-α-D-mannopyranoside 在 吡啶 、 三乙基硅烷 、 4-二甲氨基吡啶 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 2,3,4,6-tetra-O-benzoyl-1-thio-α-D-mannopyranose
  参考文献：
  名称：

  2-Haloethyl 1-Thioglycosides as New Tools in Glycoside Syntheses. Part 1: Preparation, Characteristics, General Reactions

  摘要：

  2-卤乙基1-硫代糖苷在2-卤乙基功能被银盐或Lewis酸激活时是优秀的离去基团。这些硫代糖苷可以在原始Černý路线上合成，或者为了更复杂的糖苷合成需求与之更兼容，在通过2-(2-四氢吡喃-2-氧基)乙基糖苷或三苯基1-硫代糖苷的逐步程序中合成。糖苷化反应的初始步骤可能通过硫代环氧离子进行，这对于它们在糖苷合成中作为离去基团的反应性增加具有责任。描述了这种新系统在二糖合成中的反应性和选择性的基本特征。

  DOI：

  10.1135/cccc20041843
• 作为产物：
  描述：

  三苯甲硫醇 在 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 硝基甲烷 为溶剂， 生成 triphenylmethyl 1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  A General Method for the Synthesis of Sugar 2-C-Sulfonic Acids by 1 → 2 Arylthio Group Migration in Acid-Sensitive Thioglycosides.¹ Direct Transformation of Thiotrityl Ethers into C-Sulfonic Acids

  摘要：

  Fully protected triphenylmethyl 2-O-mesyl-1-thio-beta-D-gluco- (14) and -alpha-D-mannopyranoside (28) were transformed by a stereoselective intramolecular 1 --> 2 trans-arylthio migration into methyl 2-S-triphenylmethyl-alpha-D-manno- (15) and -beta-D-glucopyranoside (29), respectively, using NaOCH3 as nucleophile. The 2-S-triphenylmethyl ethers (15 and 29) were directly oxidized to sugar 2-C-sulfonic acids by using oxone (2KHSO(5), KHSO4, K2SO4)- Compounds (21, 23, 32, and 35) are the first representatives of secondary sugar C-sulfonic acids.

  DOI：

  10.1021/ol0353518

文献信息

• Synthesis of Mannosidase-Stable Man₃ and Man₄ Glycans Containing S-linked Manα1→2Man Termini
  作者：Mahesh Neralkar、Leiming Tian、Richard L. Redman、Isaac J. Krauss

  DOI：10.1021/acs.orglett.1c00726

  日期：2021.4.16

  of interest as HIV vaccine components, but they are subject to mannosidase degradation in vivo. Herein, we report the synthesis of oligosaccharides containing a thio linkage at the nonreducing end. A thio-linked dimannose donor participates in highly stereoselective glycosylations to afford trimannose and tetramannose fragments. Saturation transfer difference nuclear magnetic resonance (STD NMR) studies

  寡甘露糖聚糖作为 HIV 疫苗成分是令人感兴趣的，但它们在体内会发生甘露糖苷酶降解。在此，我们报告了在非还原端含有硫键的寡糖的合成。硫键连接的二甘露糖供体参与高度立体选择性糖基化以提供三甘露糖和四甘露糖片段。饱和转移差异核磁共振 (STD NMR) 研究表明，这些聚糖被 HIV 抗体 2G12 识别，并且我们确认还原末端 S 键对x 具有完全的稳定性。manihotis甘露糖苷酶。
• A building block approach to the synthesis of a family of S-linked α-1,6-oligomannosides
  作者：Tyson Belz、Spencer J. Williams

  DOI：10.1016/j.carres.2016.04.015

  日期：2016.6

  The syntheses of α-1,6-S-linked methyl di-, tetra- and hexamannosides are reported. The sulfur linkages are generated through coupling of thiolates (derived from anomeric thioacetates or isothiouronium bromides) with 6-deoxy-6-iodo sugars. Two approaches are detailed that involve [2 + 2 + 2] construction from either the reducing end or the non-reducing end. In constructing from the reducing end, coupling

  报道了α-1，6-S-连接的甲基二，四和六甘露糖苷的合成。硫键是通过将硫醇盐（衍生自异头硫代乙酸盐或异硫脲溴化铵）与6-脱氧-6-碘糖偶联而生成的。详细介绍了两种方法，它们涉及从还原性端或非还原性端开始的[2 + 2 + 2]构造。在还原端的构建中，将二糖硫代乙酸盐与6'-碘还原端二糖偶联，然后将所得四糖活化为6'''-碘化物，并与相同的二糖硫代乙酸盐反复偶联，得到S-连接的六糖，以及中间的二糖和四糖。另一方面，从非还原端进行的构建涉及上述二糖硫代乙酸酯与异头S-三苯甲基保护的6'-碘二糖的偶联。将所得的S-三苯甲基四糖转化为四糖硫代乙酸酯，将其与相同的异头S-三苯甲基保护的6'-碘二糖偶联，得到六糖，将其精制为甲基硫代糖苷。所开发的方法学可能被证明可用于构建其他S-连接的寡糖。
• [EN] SULFUR-SUBSTITUTED SUGAR TO STABILIZE OLIGOSACCHARIDE<br/>[FR] SUCRE SUBSTITUÉ PAR DU SOUFRE POUR STABILISER UN OLIGOSACCHARIDE
  申请人：UNIV BRANDEIS

  公开号：WO2022197990A1

  公开（公告）日：2022-09-22

  Glycosylated peptides and oligonucleotides of the invention contain oligosaccharides that include three or more saccharide moieties, wherein two saccharide moieties at a non-reducing terminal end of the oligosaccharide are coupled together with a thio-ether bond, and one of the saccharide moieties at a reducing end of the oligosaccharide is coupled to a reactive moiety. Also disclosed are immunogenic conjugates that include a glycopeptide or oligonucleotide bound to an immunogenic carrier molecule, as well as pharmaceutical compositions containing the same.

  本发明的糖基化肽和寡核苷酸含有包括三个或更多糖基单元的寡糖，其中，在寡糖的非还原端的两个糖基单元之间通过硫醚键耦合在一起，而在寡糖的还原端之一的糖基单元与反应性基团耦合。本发明还揭示了包括糖肽或寡核苷酸结合到免疫原性载体分子上的免疫原性结合物，以及包含相同的制药组合物。
• Glycosyl azides of sugar 2-sulfonic acids
  作者：Ferenc Sajtos、László Lázár、Anikó Borbás、István Bajza、András Lipták

  DOI：10.1016/j.tetlet.2005.05.112

  日期：2005.8

  Phenyl and trityl 2-O-stilfonyl-1-thio-alpha-D-manno- and beta-D-glucopyranosides were reacted with sodium azide to yield 2-S-phenyl or 2-S-trityl-D-gluco- and D-mannopyranosyl azides, respectively. Usually, both anomers were formed in approximately equal amounts and formation of glycals was also observed in some cases. The product distribution of these reactions depends on the nature of the aglycone, the applied reagent and also on the solvent. These results can be rationalised by the intermediacy of episulfonium as well as oxocarbenium ions. Oxidation of the 2-S-trityl-alpha-D-glycopyranosyl or alpha-D-mannopyranosyl azides by Oxone (R). gave sodium 2-sulfonato-alpha-D-gluco- and alpha-D-mannopyranosyl azides, respectively. (c) 2005 Elsevier Ltd. All rights reserved.
• A General Method for the Synthesis of Sugar 2-<i>C</i>-Sulfonic Acids by 1 → 2 Arylthio Group Migration in Acid-Sensitive Thioglycosides.¹ Direct Transformation of Thiotrityl Ethers into <i>C</i>-Sulfonic Acids
  作者：András Lipták、Ferenc Sajtos、Lóránt Jánossy、Diethmar Gehle、László Szilágyi

  DOI：10.1021/ol0353518

  日期：2003.10.1

  Fully protected triphenylmethyl 2-O-mesyl-1-thio-beta-D-gluco- (14) and -alpha-D-mannopyranoside (28) were transformed by a stereoselective intramolecular 1 --> 2 trans-arylthio migration into methyl 2-S-triphenylmethyl-alpha-D-manno- (15) and -beta-D-glucopyranoside (29), respectively, using NaOCH3 as nucleophile. The 2-S-triphenylmethyl ethers (15 and 29) were directly oxidized to sugar 2-C-sulfonic acids by using oxone (2KHSO(5), KHSO4, K2SO4)- Compounds (21, 23, 32, and 35) are the first representatives of secondary sugar C-sulfonic acids.