S-thiouronium 2-N-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-D-glucopyranoside hydrochloride | 51224-18-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: S-thiouronium 2-N-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-D-glucopyranoside hydrochloride
• 英文别名: [[(2S,3R,4R,5S,6R)-3-acetamido-4,5-diacetyloxy-6-(acetyloxymethyl)oxan-2-yl]sulfanyl-aminomethylidene]azanium;chloride
• CAS: 51224-18-1
• 化学式: C₁₅H₂₃N₃O₈S*ClH
• 分子量: 441.89
• InChiKey: IFWPNCIZOWSMBN-XHNNQSHGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.31
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  192
• 氢给体数：
  4
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  S-thiouronium 2-N-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-D-glucopyranoside hydrochloride 在 吡啶 、 sodium sulfite 作用下， 以 水 、 丙酮 为溶剂， 反应 3.33h， 生成 2-acetamido-3,4,6-tri-O-acetyl-1-S-acetyl-2-deoxy-1-thio-β-D-glucopyranose
  参考文献：
  名称：

  Stereoselective synthesis of N-acetyl thiochitooligosaccharides. Different behaviours of methyl N-acetyl-α- and -β-thiochitobiosides during acetolysis

  摘要：

  A stereoselective synthesis of N-acetyl-thiochito-di-, -tri- and -tetra-saccharides is described. Coupling of methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-4-O-triflyl-beta-4 or -alpha-D-galactopyranoside 19 with 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio- beta-D-glucopranose 5 in the presence of cysteamine in DMF gave, after de-O-acylation, methyl N,N'-diacetyl-beta- 9 and -alpha-thiochitobioside 21, respectively. Different behaviours of peracetylated methyl beta- 10 and alpha-thiochitobioside 22 towards acetolysis with Ac2O-AcOH-H2SO4 solution were observed, with the beta-isomer giving acyclic sugar species together with the desired thiochitobiose peracetate 11, while the alpha-isomer gave exclusively the thiochitobiose peracetate 11. This remarkable difference between alpha- and beta-glycosides was further demonstrated by comparative acetolysis of methyl 2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-alpha- 23 and -beta-D-glucopyranoside 24. Methyl N,N',N ''-triacetylthiochitotriosides 29 and 30 were synthesized through conversion of N,N'-diacetylthiochitobiose peracetate 11 into N,N'-diacetyl-1,4-dithiochitobiose derivative 28, followed by its coupling with triflates 4 and 19 in the presence of cysteamine. Similarly, extension of the sugar chain to a higher homologue was achieved by converting methyl N,N',N ''-triacetylthiochitotrioside 30 into the N,N',N ''-triacetyl-1,4,4'-trithiochitotriose derivative 33, the coupling of which with triflate 19 in the presence of cysteamine provided the methyl N,N',N '',N triple prime-tetraacetylthiochitotetraoside 34 after de-O-acylation.

  DOI：

  10.1039/p19960000581
• 作为产物：
  描述：

  硫脲 、 2-乙酰氨基-3,4,6-三-O-乙酰-2-脱氧-α-D-吡喃葡萄糖酰基氯 以 丙酮 为溶剂， 反应 2.0h， 生成 S-thiouronium 2-N-acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-β-D-glucopyranoside hydrochloride
  参考文献：
  名称：

  抗菌素S连接糖肽Glycocin F的合成

  摘要：

  糖蛋白F是一种独特的双糖基化抗菌肽，除了O-连接的GlcNAc外，还带有一个罕见的S-连接的N-乙酰氨基葡萄糖（GlcNAc）部分，它的第一个全合成过程已经使用天然化学连接策略完成了。通过HPLC，质谱，NMR和CD光谱对合成的和天然存在的肽进行了比较，并测量了它们对胰凝乳蛋白酶消化的稳定性和抗菌活性。这是天然存在的糖蛋白与活性合成类似物的首次全面结构和功能比较。

  DOI：

  10.1002/chem.201405692

文献信息

• Thiyl Glycosylation of Olefinic Proteins: S-Linked Glycoconjugate Synthesis
  作者：Nicola Floyd、Balakumar Vijayakrishnan、Julia R. Koeppe、Benjamin G. Davis

  DOI：10.1002/anie.200903135

  日期：2009.10.5

  (homoallylglycine, Hag) as a “tag” for modification and a photoinitiated hydroglycothiolation reaction that is selective only for the Hag olefinic “tag”. Application of this method to a number of model proteins allowed complete and precise site‐selective glycosylation generating glycoconjugates that include, for example, virus‐like particles displaying up to 180 glycans at preselected positions (see scheme).

  标记为硫醇化：一种新的糖缀合策略利用非天然含烯烃的氨基酸（高烯丙基甘氨酸，Hag）作为修饰的“标签”和仅对 Hag 烯烃“标签”有选择性的光引发氢糖硫醇化反应。将此方法应用于许多模型蛋白，可以实现完整和精确的位点选择性糖基化生成糖缀合物，例如，在预选位置显示多达 180 个聚糖的病毒样颗粒（参见方案）。
• S-, N-, and O-glycosyl derivatives of 2-acetamido-2-deoxy-d-glucose with hydrophobic aglycons as potential chemotherapeutic agents and N-acetyl-β-d-glucosaminidase inhibitors
  作者：Brajeswar Paul、Walter Korytnyk

  DOI：10.1016/0008-6215(84)85124-1

  日期：1984.3

  S-, N-, and O-Glycosyl derivatives of 2-acetamido-2-deoxy-D-glucose with hydrophobic aglycons have been obtained as potential, plasma-membrane active agents. 2-Acetamido-3,4,6-tri-O-acetyl-2-deoxy-1-thio-beta-D-glucopyranose (6) was converted into benzyl, diphenylmethyl, triphenylmethyl, and other thioglycosides. Acylation of 6 gave adamantoyl and haloacetyl derivatives. A similar series of N- and

  已经获得了2-乙酰氨基-2-脱氧-D-葡萄糖与疏水性糖苷配基的S-，N-和O-糖基衍生物作为潜在的血浆膜活性剂。将2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-1-硫代-β-D-吡喃葡萄糖（6）转化为苄基，二苯甲基，三苯甲基和其他硫代糖苷。酰化6得到金刚烷基和卤代乙酰基衍生物。从相应的6的NH2-1和OH-1类似物获得了一系列类似的N-和O-糖基衍生物，例如O-和N-二硝基苯基，O-和N-金刚烷基以及N-4-甲基亚苄基衍生物。发现几种N-和S-糖基衍生物可在体外抑制小鼠的乳腺腺癌（TA3）细胞以及牛肉肝中的N-乙酰基-β-D-氨基葡萄糖苷酶。
• Preparation and Reactions of 2-Chloroethyl 1-Thio-β-D-glycopyranosides Derived from D-Galactose, D-Glucose, and 2-Acetamido-2-deoxy-D-glucose
  作者：Miloslav Černý、Tomáš Trnka、Miloš Buděšínský

  DOI：10.1135/cccc19961489

  日期：——

  Chloroethyl 1-thio-β-D-glycopyranosides of the D-galacto and D-gluco configurations 5a-5c were prepared by alkylation of the corresponding 1-thio-β-D-hexopyranoses 3a-3c with 1-bromo-2-chloroethane followed by deacetylation. The starting 1-thio-β-D-hexopyranoses were obtained from the acetylated glycopyranosyl halides via isothiouronium salts. It was demonstrated that the chloroethyl thioglycosides 5a-5c undergo hydrolysis in aqueous solutions to give the 2-hydroxyethyl thioglycosides 6a-6c and reducing hexoses and that this hydrolysis proceeds via episulfonium salts. The hydrolysis was monitored by ¹H and ¹³C NMR spectroscopy. In 1% aqueous solutions of sodium carbonate containing phenol or aniline, the thioglycosides 5a-5c provide, in addition to the above hydrolysis products, also the phenoxyethyl and phenylaminoethyl thioglycosides 9a, 10a and 9b, 10b, respectively.

  D-半乳糖 和D-葡萄糖 构型的氯乙基1-硫代-β-D-吡喃糖苷 5a-5c 通过用1-溴-2-氯乙烷烷基化相应的1-硫代-β-D-己糖吡喃糖 3a-3c，然后去乙酰化制备而成。起始的1-硫代-β-D-己糖吡喃糖是通过乙酰化的吡喃糖卤代物 经由 异硫脲盐获得的。实验证明，氯乙基硫代糖苷 5a-5c 在水溶液中发生水解，生成2-羟乙基硫代糖苷 6a-6c 和还原性己糖，并且这种水解是通过环硫銨盐进行的。水解过程通过 ¹H 和 ¹³C NMR光谱进行监测。在含酚或苯胺的1%碳酸钠水溶液中，硫代糖苷 5a-5c 除了产生上述水解产物外，还生成苯氧乙基和苯胺基乙基硫代糖苷 9a、10a和 9b、10b。
• [EN] DRUG DELIVERY<br/>[FR] ADMINISTRATION DE MÉDICAMENT
  申请人：UNIV OXFORD INNOVATION LTD

  公开号：WO2019211595A1

  公开（公告）日：2019-11-07

  A drug delivery vehicle comprising a vesicle conjugated to one or more targeting groups, wherein the targeting groups comprise an oligosaccharide which is Lewis A or Lewis B or a mimetic thereof, or a pharmaceutically acceptable salt or PEGylated form of the oligosaccharide : (I) wherein R represents the pointof attachment to the vesicle.10

  一种药物传递载体，包括与一个或多个靶向基团结合的囊泡，其中该靶向基团包括Lewis A或Lewis B或其类似物的寡糖，或者是该寡糖的药用可接受盐或PEG化形式：（I）其中R代表与囊泡的连接点。
• [EN] INFLAMMATION IMAGING AND THERAPY<br/>[FR] IMAGERIE ET THÉRAPIE D'UNE INFLAMMATION
  申请人：ISIS INNOVATION

  公开号：WO2014027203A1

  公开（公告）日：2014-02-20

  An imaging agent comprising a conjugate of an oligosaccharide moiety with an imaging moiety. The oligosaccharide is Lewis A or Lewis B or a mimetic thereof, or a pharmaceutically acceptable salt or PEGylated form of Lewis A or Lewis B or its mimetics. Lewis A and Lewis B and its mimetics are also provided for use in the therapeutic treatment of inflammatory diseases, autoimmune diseases and cancer.

  一种成像剂，包括寡糖基团与成像基团的结合物。该寡糖为Lewis A或Lewis B或其模拟物，或Lewis A或Lewis B或其模拟物的药用盐或PEG化形式。Lewis A和Lewis B及其模拟物还可用于治疗炎症性疾病、自身免疫疾病和癌症。