2-S-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-2-thiopseudourea hydrobromide | 57030-42-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-S-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-2-thiopseudourea hydrobromide
• 英文别名: tetra-O-acetyl-α-D-mannopyranosyl isothiouronium bromide；[amino-[(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]sulfanylmethylidene]azanium;bromide
• CAS: 57030-42-9
• 化学式: BrH*C₁₅H₂₂N₂O₉S
• 分子量: 487.326
• InChiKey: QNVDHERXTIAGPT-RDTZALLJSA-N

物化性质

• 熔点：
  123-126 °C(Solv: water (7732-18-5))

计算性质

• 辛醇/水分配系数(LogP)：
  0.27
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  190
• 氢给体数：
  3
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-S-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-2-thiopseudourea hydrobromide 在 tris(dibenzylideneacetone)dipalladium (0) potassium carbonate 、 三乙胺 、 三苯基膦 作用下， 以 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 3.0h， 生成 [(2R,3R,4S,5S,6R)-3,4,5-triacetyloxy-6-[3-[4-[3-[(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]sulfanylprop-1-ynyl]phenyl]prop-2-ynylsulfanyl]oxan-2-yl]methyl acetate
  参考文献：
  名称：

  Transition metal-catalyzed syntheses of ‘rod-like’ thioglycoside dimers

  摘要：

  Using copper(I)-catalyzed Glaser reaction and palladium-catalyzed Sonogashira reaction, divalent 'rod-like' thiomanno-, gluco, galacto, and lactoside clusters were prepared in high yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)02285-6
• 作为产物：
  描述：

  Α-D-五乙酸甘露糖酯 在 氢溴酸 、 溶剂黄146 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 2.5h， 生成 2-S-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-2-thiopseudourea hydrobromide
  参考文献：
  名称：

  糖病毒：化学糖基化重新靶向腺病毒基因转移。

  摘要：

  DOI：

  10.1002/anie.200461832

文献信息

• Aralkyl and aralkenyl glycosides as inhibitors of antigen-specific
  申请人：Merck & Co., Inc.

  公开号：US04554349A1

  公开（公告）日：1985-11-19

  The invention disclosed herein relates to novel 1-deoxyglycosides, preferably 1-deoxy-D-mannopyranosides and 1-deoxy-L-rhamnopyranosides, having in the 1-position of the pyranose ring an aralkylthio/aralkenylthio, aralkyloxy/aralkenyloxy or aralkanoylamino/aralkenoylamino substituent; and to novel processes for preparing these 1-substituted-1-deoxyglycosides starting with the corresponding tetra-O-acetylglycopyranosyl bromide or amine. The 6-hydroxy group of 1-substituted-1 deoxyglycopyranosides can also be replaced by other functional groups. These aralkylthio/aralkenylthio, aralkyloxy/aralkenyloxy and aralkanoylamino/aralkenoylamino 1-deoxyglycosides are potent inhibitors of antigen-specific T-cell proliferation and are also useful as inhibitors of delayed-type hypersensitivity reactions.

  本发明涉及新颖的1-去氧糖苷，优选为1-去氧-D-甘露聚糖和1-去氧-L-鼠李糖苷，在吡喃糖环的1位具有芳基硫醚/芳基烯硫醚、芳基氧/芳基烯氧或芳基酰氨基/芳基烯酰氨基取代基；以及用于制备这些1-取代-1-去氧糖苷的新工艺，从相应的四-O-乙酰基糖吡喃糖溴化物或胺开始。1-取代-1-去氧糖苷的6-羟基也可以被其他功能基团取代。这些芳基硫醚/芳基烯硫醚、芳基氧/芳基烯氧和芳基酰氨基/芳基烯酰氨基1-去氧糖苷是抗原特异性T细胞增殖的有效抑制剂，也可用作延迟型超敏反应的抑制剂。
• Preparation of anomeric pairs of 1-thioglycosides: use of anomerization catalyzed by boron trifluoride
  作者：Daniel T. Connolly、Saul Roseman、Yuan C. Lee

  DOI：10.1016/s0008-6215(00)85209-x

  日期：1980.12

  Abstract Anomeric pairs of some alkyl 1-thioaldopyranosides of d -galactose, d -glucose, d -mannose, 2-acetamido-2-deoxy- d -glucose, 2-acetamido-2-deoxy- d -galactose, and l -fucose were prepared. The per- O -acetylated, 1,2- trans anomers of 6-(trifluoroacetamido)hexyl 1-thioaldopyranosides and 5-(methoxycarbonyl)pentyl 1-thioaldopyranosides were anomerized with boron trifluoride in dichloromethane. The

  摘要d-半乳糖，d-葡萄糖，d-甘露糖，2-乙酰氨基-2-脱氧-d-葡萄糖，2-乙酰氨基-2-脱氧-d-半乳糖和l-岩藻糖的一些烷基1-硫代醛吡喃糖苷的端基对准备好了。用三氟化硼在二氯甲烷中使6-（三氟乙酰胺基）己基1-硫代吡喃吡喃糖苷和5-（甲氧基羰基）戊基1-硫代吡喃吡喃糖苷的过-O-乙酰化的1，2-反式异构体。然后使用硅胶或离子交换树脂柱通过色谱分离异头混合物。分离的化合物的解封闭提供了6-氨基己基1-硫代吡喃二糖苷或5-羧基戊基1-硫代吡喃二糖苷的纯异构体。后一种糖苷的糖苷配基通过与氨基乙醛二乙缩醛反应而进一步延伸，在产物脱缩醛化后提供ω-醛基。
• 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。
• Insulin-like, and insulin-antagonistic, carbohydrate derivatives. The synthesis of aryl and aralkyl d-mannopyranosides and 1-thio-d-mannopyranosides
  作者：Philippe L. Durette、Tsung Y. Shen

  DOI：10.1016/s0008-6215(00)85657-8

  日期：1980.5

  of novel, aryl and aralkyl D-mannopyranosides and 1-thio-D-mannopyranosides were synthesized for evaluation of insulin-like and insulin-antagonistic properties. The substituted-phenyl alpha-D-mannopyranosides were prepared by the general procedure of Helferich and Schmitz-Hillebrecht, the substituted-phenyl 1-thio-alpha-D-mannopyranosides by a method corresponding to the Michael synthesis of aromatic

  合成了许多新颖的芳基和芳烷基D-甘露糖吡喃糖苷和1-硫代-D-甘露糖吡喃糖苷，用于评估胰岛素样和胰岛素拮抗性质。通过Helferich和Schmitz-Hillebrecht的通用方法制备取代的苯基α-D-甘露糖吡喃糖苷，通过对应于芳族糖苷的迈克尔合成的方法制备取代的苯基1-硫代α-D-甘露糖吡喃糖苷，以及芳烷基。通过2,3,4,6-四-O-乙酰基-1-硫代-α-D-甘露吡喃糖的芳烷基化作用制备1-硫代-α-D-甘露吡喃糖苷（15），然后进行O-脱乙酰化。通过将2-O-乙酰基-α-D反应的产物2-S-（四-O-乙酰基-α-D-甘露吡喃糖基）-2-thiopseudourea氢溴酸盐中的mid基进行碱性裂解，得到化合物15。 -甘露糖基溴与硫脲。苄基1-硫代-β-D-甘露吡喃糖苷
• Cell-specific glycopeptide ligands
  申请人：Merck & Co., Inc.

  公开号：US04386026A1

  公开（公告）日：1983-05-31

  Cell-specific ligands comprising conjugates of saccharides and amino acids or peptides are synthesized from amino acids such as ornithine, lysine, peptides such as dilysine, diornithine or oligolysine and selected saccharides having reactive functional groups protected by appropriate blocking groups. Such glycopeptides are useful as tissue specific substances, which when coupled with bioactive materials through metabolizable or hydrolyzable linkages, deliver such bioactive materials to the selected site. In this manner, antiinflammatory drugs such as dexamethasone are linked through a metabolizable or hydrolyzable linkage and on administration to an animal suffering from inflammatory disease carries the drug to the site of inflammation for intracellular release. Other examples include the macrophage ligand N.sup.2 -N.sup.2, N.sup.6 -Bis-[3-(.alpha.-D-mannopyranosylthio)propionyl]-6-lysyl-N.sup.6 -[3-(.alpha.-D-mannopyranosylthio)propionyl]-L-lysine, 5, which when coupled to .beta.-glucocerebrosidase, can deliver the enzyme selectively to kupffer cells. This is useful in the enzyme replacement therapy of Gaucher's disease.

  由氨基酸（如鸟氨酸，赖氨酸）、肽（如双赖氨酸、双鸟氨酸或寡赖氨酸）和选定的具有适当阻断基保护的反应性官能团的糖组成的细胞特异性配体被合成。这种糖肽可用作组织特异性物质，当通过可代谢或可水解的连接与生物活性材料耦合时，可将这些生物活性材料输送到所选的部位。通过这种方式，例如，抗炎药物如地塞米松通过可代谢或可水解的连接与之链接，并在对患有炎症性疾病的动物进行治疗时将药物带到炎症部位进行细胞内释放。其他例子包括巨噬细胞配体N.sup.2-N.sup.2，N.sup.6-Bis-[3-(.alpha.-D-mannopyranosylthio)propionyl]-6-lysyl-N.sup.6-[3-(.alpha.-D-mannopyranosylthio)propionyl]-L-lysine，5，当与β-葡聚糖酶耦合时，可以将酶有选择地输送到库普弗细胞。这在高氏病的酶替代疗法中非常有用。