N-(2,2-diethoxycarbonylvinyl)-β-D-mannopyranosylamine | 22435-75-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-(2,2-diethoxycarbonylvinyl)-β-D-mannopyranosylamine
• 英文别名: diethyl 2-[[[(2R,3S,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]amino]methylidene]propanedioate
• CAS: 22435-75-2
• 化学式: C₁₄H₂₃NO₉
• 分子量: 349.338
• InChiKey: XUYUHPVSRYKWPB-LDMBFOFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  155
• 氢给体数：
  5
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  N-(2,2-diethoxycarbonylvinyl)-β-D-mannopyranosylamine 在 吡啶 、 sodium methylate 、 氯 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 50.0 ℃ 、2.67 kPa 条件下， 反应 100.58h， 生成 (3R,4R,5R,6R)-3,4,5,6-Tetrahydroxyazepane
  参考文献：
  名称：

  An easy route to seven-membered iminocyclitols from aldohexopyranosyl enamines

  摘要：

  A new stereocontrolled and high yielding synthesis of biologically active polyhydroxyperhydroazelpines is reported starting from easily available glycosylenamines (D-gluco, D-manno, and D-galacto configurations), which are transformed into 1,6-azaanhydropyranose derivatives. O- and N-Deprotection of the latter, followed by reduction with sodium cyanoborohydride, gives the target chiral iminocyclitols. The method is based on the capacity of the dialkoxycarbonylvinyl group to stabilize an amide ion, and the only limitation is the necessity for the starting glycosylenamine to have beta-D-configuration. The inhibitory activity of several intermediate iminocyclitols and aldopyranosylenamines on different alpha- and beta-glycosidases is also reported. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00377-4
• 作为产物：
  描述：

  1-氨基-1-脱氧-beta-D-吡喃甘露糖 、 乙氧基甲叉丙二酸二乙酯 以 甲醇 为溶剂， 以71%的产率得到N-(2,2-diethoxycarbonylvinyl)-β-D-mannopyranosylamine
  参考文献：
  名称：

  （1→6）-硫脲连接的假寡糖的合成及端基稳定性

  摘要：

  摘要报道了通过单-和二糖-过-O-乙酰化的糖基异硫氰酸酯与甲基6-氨基-6-脱氧-α-d-吡喃葡萄糖苷的偶联合成掺入硫脲糖间桥联的寡糖模拟物的方法。然而，在Zemplen脱乙酰基作用下，对于α-和β-d-甘露吡喃糖基硫脲基衍生物，观察到了意外的异构化反应。动力学研究表明，该异构化过程是碱催化的，并且强烈依赖于反应温度和反应时间。通过在0°C下进行最后一步，可以在没有差向异构的情况下获得完全未保护的化合物。在所有情况下，最终的伪低聚糖在室温下在没有碱的情况下在水溶液中都是稳定的。

  DOI：

  10.1016/s0008-6215(99)00141-x

文献信息

• Ring contraction of glycopyranosyl enamines: an easy route to furanoid thioglycosides of 5-aminosugars
  作者：M.Ángeles Pradera、Francisco J. Sayago、José M. Illangua、Manuel Angulo、Consolación Gasch、José Fuentes

  DOI：10.1016/j.tetasy.2004.05.027

  日期：2004.7

  The reaction of glycohexapyranosyl enamines, having 2- and 3-hydroxyl groups in a cis-relationship with 12-dimethoxypropane, induces ring contraction of the sugar ring with formation of 2,3-O-isopropylidene furanoid glycosylenamines. 5-O-Mesylation of these compounds. followed by formation of anhydroazasugars and nucleophilic ring opening, with thiols, produces alkyl and aryl thiofuranosides of 5-aminosugars. (C) 2004 Elsevier Ltd. All rights reserved.
• Synthesis and anomeric stability of (1→6)-thiourea-linked pseudooligosaccharides
  作者：Juan Manuel Benito、Carmen Ortiz Mellet、Kashinath Sadalapure、Thisbe K Lindhorst、Jacques Defaye、José Manuel Garcı́a Fernández

  DOI：10.1016/s0008-6215(99)00141-x

  日期：1999.7

  per-O-acetylated glycosyl isothiocyanates and methyl 6-amino-6-deoxy-α- d -glucopyranoside, is reported. An unexpected anomerization reaction was observed, however, for α- and β- d -mannopyranosylthioureido derivatives upon Zemplen deacetylation. Kinetics studies revealed that this anomerization process is base catalysed and strongly dependent upon reaction temperature and reaction time. The fully unprotected compounds

  摘要报道了通过单-和二糖-过-O-乙酰化的糖基异硫氰酸酯与甲基6-氨基-6-脱氧-α-d-吡喃葡萄糖苷的偶联合成掺入硫脲糖间桥联的寡糖模拟物的方法。然而，在Zemplen脱乙酰基作用下，对于α-和β-d-甘露吡喃糖基硫脲基衍生物，观察到了意外的异构化反应。动力学研究表明，该异构化过程是碱催化的，并且强烈依赖于反应温度和反应时间。通过在0°C下进行最后一步，可以在没有差向异构的情况下获得完全未保护的化合物。在所有情况下，最终的伪低聚糖在室温下在没有碱的情况下在水溶液中都是稳定的。
• An easy route to seven-membered iminocyclitols from aldohexopyranosyl enamines
  作者：José Fuentes、Consolación Gasch、David Olano、M.Ángeles Pradera、Guillermo Repetto、Francisco J. Sayago

  DOI：10.1016/s0957-4166(02)00377-4

  日期：2002.8

  A new stereocontrolled and high yielding synthesis of biologically active polyhydroxyperhydroazelpines is reported starting from easily available glycosylenamines (D-gluco, D-manno, and D-galacto configurations), which are transformed into 1,6-azaanhydropyranose derivatives. O- and N-Deprotection of the latter, followed by reduction with sodium cyanoborohydride, gives the target chiral iminocyclitols. The method is based on the capacity of the dialkoxycarbonylvinyl group to stabilize an amide ion, and the only limitation is the necessity for the starting glycosylenamine to have beta-D-configuration. The inhibitory activity of several intermediate iminocyclitols and aldopyranosylenamines on different alpha- and beta-glycosidases is also reported. (C) 2002 Published by Elsevier Science Ltd.