甲基2-乙酰氨基-4,6-O-亚苄基-2-脱氧吡喃己糖苷 | 10300-76-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 中文名称: 甲基2-乙酰氨基-4,6-O-亚苄基-2-脱氧吡喃己糖苷
• 英文名称: methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
• 英文别名: methyl-[2-acetylamino-O⁴,O⁶-((Ξ)-benzylidene)-2-deoxy-β-D-glucopyranoside]；Methyl-[2-acetylamino-O⁴,O⁶-((Ξ)-benzyliden)-2-desoxy-β-D-glucopyranosid]；Methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-b-D-glucopyranoside；N-[(4aR,6R,7R,8R,8aS)-8-hydroxy-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]acetamide
• CAS: 10300-76-2
• 化学式: C₁₆H₂₁NO₆
• 分子量: 323.346
• InChiKey: XCDVOAZVARITEI-ANNNQLRWSA-N

物化性质

• 熔点：
  296-298 °C
• 沸点：
  579.4±50.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  86.2
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  甲基2-乙酰氨基-4,6-O-亚苄基-2-脱氧吡喃己糖苷 在 potassium hydroxide 作用下， 以 水 为溶剂， 反应 24.0h， 以77%的产率得到methyl 2-amino-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  氨基葡萄糖乙烯基醚衍生物及其氘代类似物的合成

  摘要：

  在超碱性条件（KF、KOH）下使用碳化钙（在 H2O 存在下）作为乙炔来源与甲基 2-氨基-4,6-O-苄叉-2-脱氧-β-d-吡喃葡萄糖苷反应, DMSO, 130 °C, 3 h) 产生相应的乙烯基醚，产率为 78%。乙烯基化不影响其他反应中心。在反应混合物中用氧化氘代替水得到稳定的这种乙烯基醚的氘代类似物，产率为 72%。一步同位素富集实际上是定量的（同位素纯度 > 96%）。引入的氘原子可用作进一步转化中的方便标记。

  DOI：

  10.1007/s11172-020-2915-3
• 作为产物：
  描述：

  D-glucosamine hydrochloride 在 iron(III) chloride 、 sodium methylate 、 对甲苯磺酸 、 zinc(II) chloride 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 77.33h， 生成 甲基2-乙酰氨基-4,6-O-亚苄基-2-脱氧吡喃己糖苷
  参考文献：
  名称：

  氨基葡萄糖乙烯基醚衍生物及其氘代类似物的合成

  摘要：

  在超碱性条件（KF、KOH）下使用碳化钙（在 H2O 存在下）作为乙炔来源与甲基 2-氨基-4,6-O-苄叉-2-脱氧-β-d-吡喃葡萄糖苷反应, DMSO, 130 °C, 3 h) 产生相应的乙烯基醚，产率为 78%。乙烯基化不影响其他反应中心。在反应混合物中用氧化氘代替水得到稳定的这种乙烯基醚的氘代类似物，产率为 72%。一步同位素富集实际上是定量的（同位素纯度 > 96%）。引入的氘原子可用作进一步转化中的方便标记。

  DOI：

  10.1007/s11172-020-2915-3

文献信息

• Synthesis of various glycosides of 2-amino-3-O-D-1-carboxyethyl)-2-deoxy-D-glucopyranose (muramic acid)
  作者：Roger W. Jeanloz、Evelyne Walker、Pierre Sinaÿ

  DOI：10.1016/s0008-6215(00)81509-8

  日期：1968.2

  with that obtained from methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-β- D -glucopyranoside. Benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-[ D -1-(methoxycarbonyl)ethyl]-β- D -glucopyranoside was also obtained by condensation with pure L -chloropropionic acid. Benzyl and p-nitrophenyl 2-acetamido-3-O-( D -1-carboxyethyl)-2-deoxy-β- D -glucopyranoside were resistant to the action of egg-white lysozyme

  摘要2-乙酰氨基-4,6-O-亚苄基-2-脱氧-α-D-吡喃葡萄糖苷，甲基，苄基和对硝基苯基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-β -D-吡喃葡萄糖苷与DL -2-氯丙酸缩合，以优异的收率（分别为64、46、68和25％）得到各自的3-O-（D -1-羧乙基）衍生物，分离为他们的甲酯。仅从甲基α-D-葡糖苷的缩合中分离出显着比例（11％收率）的3-O-（L -1-羧乙基）衍生物。将2-乙酰氨基-4,6-二-O-乙酰基-2-脱氧-3-O-[（D -1-甲氧羰基）乙基]-α-D-吡喃葡萄糖苷的乙酰化反应得到恶唑啉; 先用氢溴酸在乙酸中处理，然后再用氧化银和甲醇处理，得到与从2-乙酰氨基-4，6-O-亚苄基-2-脱氧-β-D-吡喃葡萄糖苷甲基获得的β-D-葡萄糖苷甲基相同的甲基β-D-葡萄糖苷衍生物。苄基2-乙酰氨基-4,6-O-亚苄基-2-脱氧-3-O- [D -1-（甲氧羰基）乙基]
• Nikrad, P. V.; Beierbeck, H.; Lemieux, R. U., Canadian Journal of Chemistry, 1992, vol. 70, # 1, p. 241 - 253
  作者：Nikrad, P. V.、Beierbeck, H.、Lemieux, R. U.

  DOI：——

  日期：——
• Constrained H-Type 2 Blood Group Trisaccharide Synthesized in a Bioactive Conformation via Intramolecular Glycosylation
  作者：Shirley A. Wacowich-Sgarbi、David R. Bundle

  DOI：10.1021/jo990979a

  日期：1999.12.1

  The methyl glycoside of the II-type 2 trisaccharide 1 was synthesized in a constrained, bioactive conformation via intramolecular aglycon delivery. Computer modeling of the crystal structure of the Ulex europaeus I lectin with a docked H-type 2 trisaccharide suggested that the disaccharide Galp(1-->4)GlcpNAc1-->OCH3 could be tethered in a bioactive conformation if Gal O-6 and GlcNAc O-3 are linked via a three-carbon tether. The ethyl 1-thiogalactopyranoside 13 was used to alkylate the methyl 2-acetamido-2-deoxy glucopyranoside 7, and the resulting dimer was subjected to intramolecular glycosylation following protecting group manipulation. The tethered disaccharide 4 was glycosylated by the activated fucopyranosyl donor 3 to give the protected target molecule 17. Solid-phase binding assays showed that the tethered trisaccharide 2 was 3-fold less active than native II-type 2 trisaccharide 1 when assayed against the U, europaeus I lectin, whereas it was 250 times less active when assayed with the Psophocarpus tetragonolobus II lectin. The observed activities are consistent with published models for H-trisaccharide interactions with Ulex: and Psophocarpus lectins and provide further evidence that suggests reduction of oligosaccharide flexibility by intramolecular tethering provides no significant gain in binding energy.
• A General Procedure for One-Pot Benzylidenation and Methyl (or Benzyl) Glycosidation of Aldoses
  作者：Jean-Claude Florent、Claude Monneret

  DOI：10.1055/s-1982-29688

  日期：——
• Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for the<i>Shigella flexneri</i>Serotype 2a<i>O</i>-Antigen
  作者：Laurence A. Mulard、Corina Costachel、Philippe J. Sansonetti

  DOI：10.1080/07328300008544123

  日期：2000.1

  The stereocontrolled synthesis of methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranoside (EC, 1), methyl alpha-L-rhamnopyranosyl-(1-->3)-[alpha-D-glucopyra- osyl-(1-->4)]-alpha-L-rhamnopyranoside (B(E)C, 3) and methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-2-acetamido-2-deoxy-beta-D-glucopyranoside (ECD, 4) is described; these constitute the methyl glycosides of branched and linear fragments of the O-specific polysaccharide of Shigella flexneri serotype 2a. Emphasis was put on the construction of the 1,2-cis EC glycosidic linkage resulting in the selection of 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl fluoride (8) as the donor. Condensation of methyl 2,3-O-isopropylidene-4-O-trimethylsilyloside-alpha-L-rhamnopyranoside (11) and 8 afforded the fully protected alpha E-disaccharide 20, as a common intermediate in the synthesis of 1 and 3, together with the corresponding beta E-anomer 21. Deacetalation and regioselective benzoylation of 20, followed by glycosylation with 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (15) afforded the branched trisaccharide 25. Full deprotection of 20 and 25 afforded the targets 1 and 3, respectively. The corresponding beta E-disaccharide, namely, methyl beta-D-glucopyranosyl-(1-->4)-a-L-rhamnopyranoside (PEC, 2) was prepared analogously from 21. Two routes to trisaccharide 4 were considered. Route 1 involved the coupling of a precursor to residue E and a disaccharide CD. Route 2 was based on the condensation of an appropriate EC donor and a precursor to residue D. The former route afforded a 1:2 mixture of the alpha E and PE condensation products which could not be separated, neither at this stage, nor after deacetalation. In route 2, the required alpha E-anomer was isolated at the disaccharide stage and transformed into 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl-(1-->4)-2,3-di-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (48) as the EC donor. Methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-beta-D-glucopyran-oside (19) was preferred to its benzylidene analogue as the precursor to residue D. Condensation of 19 and 48 and stepwise deprotection of the glycosylation product afforded the target 4.