phenyl 2,3-di-O-benzyl-4,6-O-di-tert-butylsilylene-1-thio-β-D-galactopyranoside | 911815-94-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2,3-di-O-benzyl-4,6-O-di-tert-butylsilylene-1-thio-β-D-galactopyranoside
• 英文别名: (4aR,6S,7R,8R,8aS)-2,2-ditert-butyl-7,8-bis(phenylmethoxy)-6-phenylsulfanyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3,2]dioxasiline
• CAS: 911815-94-6
• 化学式: C₃₄H₄₄O₅SSi
• 分子量: 592.872
• InChiKey: CICBATZHQGPWHV-MQSWGENCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.13
• 重原子数：
  41
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  71.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  phenyl 2,3-di-O-benzyl-4,6-O-di-tert-butylsilylene-1-thio-β-D-galactopyranoside 在 N-溴代丁二酰亚胺(NBS) 、 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以78%的产率得到2,3-di-O-benzyl-4,6-di-tert-butylsilylene-α-D-galactopyranosyl fluoride
  参考文献：
  名称：

  Synthetic studies on the carbohydrate moiety of the antigen from the parasite Echinococcusmultilocularis

  摘要：

  Stereocontrolled syntheses of branched tri-, tetra-, and pentasaccharides displaying a Gal beta 1 -> 3GalNAc core in the glycan portion of the glycoprotein antigen from the parasite Echinococcus multilocularis have been accomplished. Trisaccharide Gal beta 1 -> 3(GlcNAc beta 1 -> 6)GalNAc alpha 1-OR (A). tetrasaccharide Gal beta 1 -> 3(Gal beta 1 -> 4Gal beta 1 -> 6)GalNac alpha 1-OR(D), and pentasaccharides Gal beta 1 -> 3(Gal beta 1 -> 4Gal beta 1 -> 4Gl cNAc beta 1-6)GalNAc alpha 1-OR (E) and Gal beta 1-3(Gal alpha 1 -> 4Gal alpha 1 -> 4Gal alpha 1 -> 6)GalNAc alpha 1-OR) (F) (R = 2(trimethylsilyl)ethyl) were synthesized by block synthesis. The disaccharide 2-(trimethylsilyl)ethyl 2,3,4,6-tetra-O-acetyl-P-D-galactopyranosyl-(1 -> 3)-2-azido-4-O-benzyl-2-deoxy-alpha-D-galactopyranoside served as a common glycosyl acceptor in the synthesis of the branched oligosaccharicles. Moreover, linear trisaccharide Gal beta 1 -> Gal beta 1 -> 3GalNac alpha 1-OR (B) and branched tetrasaccharide Gal beta 1 -> Gal beta 1 -> 3(GalNac beta 1 -> 6)GalNac alpha 1-OR (C) were synthesized by stepwise condensation. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2009.02.019
• 作为产物：
  描述：

  二叔丁基硅基双(三氟甲烷磺酸) 、 phenyl 2,3-di-O-benzyl-1-thio-β-D-galactopyranoside 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.25h， 以85.7%的产率得到phenyl 2,3-di-O-benzyl-4,6-O-di-tert-butylsilylene-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Stereoselective synthesis of 1,2-cis galactosides: synthesis of a glycolipid containing Galα1-6Gal component from Zygomycetes species

  摘要：

  An alpha-selective galactosylation was demonstrated under various conditions. Among these alpha-galactoside approaches, high a-selectivity was achieved by the virtue of 4,6-O-di-tert-butylsitylene (DTBS) group. Yield was further improved by the influence of a 2-O-benzylated donor compared to 2-O-benzoylated donor. This method was then applied to the first highly stereoselective synthesis of a newly found trisaccharide glycosphingolipid in Zygomycetes species. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.06.181

文献信息

• Pentavalent Bismuth as a Universal Promoter for S-Containing Glycosyl Donors with a Thiol Additive
  作者：Daniel E. K. Kabotso、Nicola L. B. Pohl

  DOI：10.1021/acs.orglett.7b02080

  日期：2017.9.1

  S-Propyl glycosides of less activated sugars, such as peracetylated carbohydrates and uronic acid esters that could not previously be activated with triphenylbismuth ditriflate alone, were found to be glycosylated in the presence of propanethiol as an additive in under 3 h. This newly developed protocol was also found to be effective in promoting glycosylation of neutral and uronic acid esters of S-phenyl

  发现在三小时内在丙硫醇作为添加剂存在下，活化程度较低的糖（例如过乙酰化的碳水化合物和糖醛酸酯类）的S-丙基糖苷以前无法单独用三苯基铋三氟甲磺酸酯活化，因此被糖基化。还发现该新开发的方案可有效促进S-苯基，S-噻唑啉基，S-苯并恶唑基和S-金刚烷基糖苷以及唾液酸的中性和糖醛酸酯的糖基化。
• Synthesis of the Carbohydrate Moiety of Glycoproteins from the Parasite Echinococcus granulosus and Their Antigenicity against Human Sera
  作者：Noriyasu Hada、Tokio Morita、Takashi Ueda、Kazuki Masuda、Hiromi Nakane、Mami Ogane、Kimiaki Yamano、Frank Schweizer、Fumiyuki Kiuchi

  DOI：10.3390/molecules26185652

  日期：——

  6-O-benzylidene-2-deoxy-α-d-galactopyranoside as a common glycosyl acceptor. The synthesis of the tetrasaccharide and the pentasaccharide was improved from the viewpoint of reducing the number of synthetic steps and increasing the total yield by changing from stepwise condensation to block synthesis. Moreover, hexasaccharide E, which contains the oligosaccharide sequence which occurs in E. granulosus

  含有细粒棘球绦虫糖蛋白碳水化合物部分的生物素标记寡糖部分的立体控制合成已经完成。三糖 Galβ1-3Galβ1-3GalNAcα1-R ( A )、四糖 Galα1-4Galβ1-3Galβ1-3GalNAcα1-R ( B ) 和五糖 Galα1-4Galβ1-3Galβ1-3Galβ1-3GalNAcα1-R ( C )，（R = 生物素化探针）使用5-(甲氧基羰基)戊基2-叠氮基-4,6- O-亚苄基-2-脱氧-α- d-吡喃半乳糖苷作为常见糖基受体，通过逐步缩合和/或嵌段合成法合成。通过从逐步缩合变为嵌段合成，从减少合成步骤数和增加总收率的角度来看，改进了四糖和五糖的合成。此外，由三糖D合成了六糖E ，其含有细粒棘球绦虫中存在的寡糖序列。我们通过酶联免疫吸附测定（ELISA）检查了这五种寡糖的抗原性。虽然C – E化合物对囊性包虫病 (CE) 患者血清不表现出抗原性，但化合物B 、
• Synthesis of Glycosylated 1-Deoxynojirimycins Starting from Natural and Synthetic Disaccharides
  作者：Bing Liu、Jeanine van Mechelen、Richard J. B. H. N. van den Berg、Adrianus M. C. H. van den Nieuwendijk、Johannes M. F. G. Aerts、Gijsbert A. van der Marel、Jeroen D. C. Codée、Herman S. Overkleeft

  DOI：10.1002/ejoc.201801461

  日期：2019.1.10

  Iminosugars are an important class of natural products and have been subject to extensive studies in organic synthesis, bioorganic chemistry and medicinal chemistry, yet only a limited number of these studies are on glycosylated iminosugars. Here, a general route of synthesis is presented towards glycosylated 1‐deoxynojirimycin derivatives based on the oxidation–reductive amination protocol that in

  亚氨基糖是一类重要的天然产物，在有机合成、生物有机化学和药物化学方面得到了广泛的研究，但这些研究中只有少数是关于糖基化亚氨基糖的。在这里，提出了基于氧化还原胺化方案的糖基化 1-脱氧野尻霉素衍生物的一般合成路线，该方案在过去也被证明是合成 1-脱氧野尻霉素的通用途径。该策略可应用于商业二糖，如四个示例所示，也可应用于非市售二糖，并为此目的合成，如第五个示例所示。
• Synthesis and Structural Analysis of <i>Aspergillus fumigatus</i> Galactosaminogalactans Featuring α‐Galactose, α‐Galactosamine and α‐ <i>N</i> ‐Acetyl Galactosamine Linkages
  作者：Yongzhen Zhang、Marcos Gómez‐Redondo、Gonzalo Jiménez‐Osés、Ana Arda、Herman S. Overkleeft、Gijsbert A. Marel、Jesús Jiménez‐Barbero、Jeroen D. C. Codée

  DOI：10.1002/anie.202003951

  日期：2020.7.27

  oligomers by a combination of NMR and MD approaches revealed that the oligomers adopt an elongated, almost straight, structure, stabilized by inter‐residue H‐bonds, one of which is a non‐conventional C−H⋅⋅⋅O hydrogen bond between H5 of the residue (i +1) and O3 of the residue (i ). The structures position the C‐2 substituents almost perpendicular to the oligosaccharide main chain axis, pointing to the bulk

  半乳糖氨基半乳聚糖（GAG）是机会性真菌病原体烟曲霉的重要细胞壁成分。GAG是由α-1,4-连接的半乳​​糖，半乳糖胺和N-乙酰半乳糖胺残基组成的杂多糖。为了进行生化研究，构建了一个包含有α-半乳糖，α-半乳糖胺和α- N-乙酰半乳糖胺键的标本的GAG片段库。合成策略的主要特点包括采用二的叔-丁基亚甲硅烷基定向的α-半乳糖基化方法和使用苯甲酰基-羟基苯并三唑（Bz-OBt）的区域选择性苯甲酰化反应。通过结合NMR和MD方法对Gal，GalN和GalNAc低聚物进行结构分析，结果表明这些低聚物采用细长的，几乎笔直的结构，并通过残基间的氢键稳定，其中之一是非常规C残余物的H5之间H⋅⋅⋅O氢键（我1）和残留物（的O3我）。该结构将C-2取代基定位成几乎垂直于寡糖主链轴，指向主体溶剂，可用于与抗体或其他结合伴侣的相互作用。
• Synthesis of the Highly Branched Hexasaccharide Core of Chlorella Virus <i>N</i> ‐Linked Glycans
  作者：Sicheng Lin、Todd L. Lowary

  DOI：10.1002/chem.201804795

  日期：2018.11.16

  and structurally‐unprecedented glycans requires access to probe molecules. This work describes the first synthesis of a chlorella virus N‐linked glycan, a highly branched hexasaccharide that contains the pentasaccharide present in all of the >15 structures reported to date. The target molecule includes a glucosyl‐asparagine linkage and a “hyperbranched” fucose residue in which all of the hydroxyl groups

  小球藻病毒产生的N连接糖蛋白的碳水化合物部分与所有其他N连接聚糖的结构不同。另外，与大多数病毒不同，这些生物不会劫持宿主的生物合成机制来制造糖蛋白。相反，它们产生自己的碳水化合物加工酶。要更好地了解这些引人入胜的，结构上前所未有的聚糖的功能和组装，需要使用探针分子。这项工作描述了小球藻病毒N的首次合成-连接的聚糖，一种高度分支的六糖，包含迄今为止报道的所有> 15个结构中的五糖。目标分子包括一个葡萄糖基-天冬酰胺键和一个“超支链”岩藻糖残基，其中所有羟基均被糖基化。研究了收敛和线性方法，后者成功地以16个步骤提供了目标，总产率为13％。