2,3,4-tri-O-acetyl-6-O-[2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl]-β-D-glucopyranosyl azide | 133272-39-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4-tri-O-acetyl-6-O-[2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl]-β-D-glucopyranosyl azide
• 英文别名: 1-azido-1-deoxy-6-O-(2',3',4',6'-tetra-O-acetyl-α-D-galactopyranosyl)-2,3,4-tri-O-acetyl-β-D-glucose；Gal2Ac3Ac4Ac6Ac(a1-6)Glc2Ac3Ac4Ac(b)-N3；[(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-azidooxan-2-yl]methoxy]oxan-2-yl]methyl acetate
• CAS: 133272-39-6
• 化学式: C₂₆H₃₅N₃O₁₇
• 分子量: 661.574
• InChiKey: GVXPEXAJLBXROU-NBAXBWOSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  46
• 可旋转键数：
  19
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  226
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  2,3,4-tri-O-acetyl-6-O-[2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl]-β-D-glucopyranosyl azide 在 三苯基膦 作用下， 以 1,2-二氯乙烷 为溶剂， 生成
  参考文献：
  名称：

  Stereoselective Synthesis of α- and β-Glycosylamide Derivatives from Glycopyranosyl Azides via Isoxazoline Intermediates

  摘要：

  Treatment of 2-acetoxy glycopyranosyl azides with Ph3P gave isoxazolines by ring closure of the phosphorimine. Coupling of in situ generated isoxazolines with acylating reagents gave mixtures of alpha- or beta-glycopyranosyl amides. The alpha/beta ratio depended upon the acylating reagent and metal salts employed. For example, coupling of isoxazoline 3 with Z-Asp-(SPy)-OBn in the presence of CuCl2 gave exclusively alpha-N-glucopyranosylasparagine derivative 8. This general procedure has been applied to mono-, di-, and trisaccharide systems.

  DOI：

  10.1021/ja028694u
• 作为产物：
  描述：

  melibioseperacetate 在 叠氮基三甲基硅烷 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以74%的产率得到2,3,4-tri-O-acetyl-6-O-[2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl]-β-D-glucopyranosyl azide
  参考文献：
  名称：

  Stereoselective Synthesis of α- and β-Glycosylamide Derivatives from Glycopyranosyl Azides via Isoxazoline Intermediates

  摘要：

  Treatment of 2-acetoxy glycopyranosyl azides with Ph3P gave isoxazolines by ring closure of the phosphorimine. Coupling of in situ generated isoxazolines with acylating reagents gave mixtures of alpha- or beta-glycopyranosyl amides. The alpha/beta ratio depended upon the acylating reagent and metal salts employed. For example, coupling of isoxazoline 3 with Z-Asp-(SPy)-OBn in the presence of CuCl2 gave exclusively alpha-N-glucopyranosylasparagine derivative 8. This general procedure has been applied to mono-, di-, and trisaccharide systems.

  DOI：

  10.1021/ja028694u

文献信息

• Synthesis of N-(fluoren-9-ylmethoxycarbonyl)glycopyranosylamine uronic acids
  作者：Laiqiang Ying、Jacquelyn Gervay-Hague

  DOI：10.1016/j.carres.2003.10.018

  日期：2004.1

  The synthesis of 10 N-(fluoren-9-ylmethoxycarbonyl)glycopyranosylamine uronic acids that are amenable to solid-phase synthesis is described. The general synthetic strategy involves initial incorporation of the protected amine, followed by selective TEMPO oxidation of C-6 hydroxyl groups to give the corresponding Fmoc-protected sugar amino acids. Amine incorporation may be accomplished from aminolysis

  描述了适于固相合成的10种N-（氟-9-基甲氧基羰基）甘露糖基氨基糖醛酸的合成。一般的合成策略包括首先引入受保护的胺，然后对C-6羟基进行TEMPO选择性氧化，得到相应的Fmoc保护的糖氨基酸。胺的掺入可通过游离糖的氨解或糖基叠氮化物的还原来完成。该反应可以以多克级进行，从而提供了访问独特单体单元的途径，以便将来将其并入组合文库合成中。
• New ureas containing glycosyl and diphenylphosphinyl scaffolds: synthesis and the first attempts to use them in asymmetric synthesis
  作者：Stanisław Porwański

  DOI：10.1016/j.carres.2014.04.015

  日期：2014.7

  Chiral ureas containing glycosyl and diphenylphosphinyl scaffolds were found to be an effective organocatalyst. They were synthesised in high yields by a one-pot tandem Staudinger/aza-Wittig coupling reaction. The first attempts of using them in asymmetric synthesis are presented. Yields of the Morita-Baylis-Hillman reaction were moderate with an enantiomeric excess of up to 80%.

  发现含有糖基和二苯基膦基骨架的手性脲是有效的有机催化剂。它们通过一锅串联Staudinger / aza-Wittig偶联反应以高收率合成。提出了在不对称合成中使用它们的首次尝试。Morita-Baylis-Hillman反应的产率中等，对映体过量高达80％。
• General methods for the synthesis of glycopyranosyluronic acid azides
  作者：Laiqiang Ying、Jacquelyn Gervay-Hague

  DOI：10.1016/s0008-6215(03)00042-9

  日期：2003.4

  converted to glycosyl iodides and subsequently reacted with an azide source to achieve the stereoselective synthesis of beta-D-glycosyl azides after deacetylation. Low-temperature (4 degrees C) TEMPO oxidation of the monosaccharides provided the corresponding uronic acids, which were purified as the free acids. Oxidation of the lactosyl- and cellobiosyl azides resulted in diacid formation. However, 4',6'-O-benzylidene

  首先将衍生自单糖和二糖的过-O-乙酰化D-甘露聚糖转化为糖基碘，然后与叠氮化物源反应，以在脱乙酰基反应后实现立体选择性合成β-D-糖基叠氮化物。单糖的低温（4摄氏度）TEMPO氧化提供了相应的糖醛酸，其被纯化为游离酸。乳糖基和纤维二糖叠氮化物的氧化导致二酸形成。然而，4'，6'-O-亚苄基保护能够选择性氧化C-6羟基。还制备了2-乙酰胺基-2-脱氧-D-甘露糖基叠氮化物，并将其转化为糖醛酸，从而完成了文库的合成。
• New sugar-derived bifunctional chiral ureas as highly effective organocatalysts in asymmetric aza-Henry reaction
  作者：Jolanta Robak、Bogusław Kryczka、Barbara Świerczyńska、Anna Zawisza、Stanisław Porwański

  DOI：10.1016/j.carres.2014.11.019

  日期：2015.3

  A simple synthesis of series of new catalysts derived from chiral bifunctional ureas is described. The aza-Henry reaction of imines with nitromethane was promoted by sugar derived bifunctional organocatalysts to give optically active beta-nitroamines. The aza-Henry reaction products were obtained in good yields (35-98%) and ee up to 99%.

  描述了衍生自手性双官能脲的一系列新催化剂的简单合成。糖衍生的双官能有机催化剂可促进亚胺与硝基甲烷的氮杂-亨利反应，从而生成光学活性的β-硝基胺。以良好的产率（35-98％）和高达99％的ee获得了氮杂-亨利反应产物。
• Peto, Csaba; Batta, Gyula; Gyoergydeak, Zoltan, Liebigs Annalen der Chemie, 1991, # 5, p. 505 - 507
  作者：Peto, Csaba、Batta, Gyula、Gyoergydeak, Zoltan、Sztaricskai, Ferenc

  DOI：——

  日期：——