methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 2-(N-phenyl)trifluoroacetimidate | 874904-90-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 2-(N-phenyl)trifluoroacetimidate
• 英文别名: methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosylonate N-phenyltrifluoroacetimidate；methyl (4S,5R,6R)-5-acetamido-4-acetyloxy-2-[N-phenyl-C-(trifluoromethyl)carbonimidoyl]oxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 874904-90-2
• 化学式: C₂₈H₃₃F₃N₂O₁₃
• 分子量: 662.571
• InChiKey: DXTDONNXMSROFM-MXBFFZHUSA-N

物化性质

• 密度：
  1.38±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  46
• 可旋转键数：
  17
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  191
• 氢给体数：
  1
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 2-(N-phenyl)trifluoroacetimidate 在 三氟甲磺酸三甲基硅酯 、 C₂₂H₂₉NO₁₀S 作用下， 以 丙腈 为溶剂， 以90%的产率得到methyl-2,3-didehydro-4,7,8,9-tetra-O-acetyl-N-acetylneuraminate
  参考文献：
  名称：

  Reinvestigation of the C5-acetamide sialic acid donor for α-selective sialylation: practical procedure under microfluidic conditions

  摘要：

  尽管之前的文献描述了 "低至最低 "的效率，但我们还是重新研究了在微流体条件下δ-ialylation中使用的现成的C5-乙酰胺供体。N- 苯基三氟乙酰亚氨酸供体与适量的 TMSOTf 有效混合后，可生成半乳糖和葡萄糖胺受体的δ(2â6)和δ(2â3)-硅烷基化产物，产率极高，且具有近乎完美的δ选择性。

  DOI：

  10.1039/c1ob06164j
• 作为产物：
  描述：

  2,2,2-三氟-N-苯基亚氨代乙酰氯 、 methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-2,3-dideoxy-D-glycero-D-galacto-2-nonulopyranosate 在 potassium carbonate 作用下， 以 丙酮 为溶剂， 生成 methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-D-galacto-2-nonulopyranosonate 2-(N-phenyl)trifluoroacetimidate
  参考文献：
  名称：

  Highly Efficient α‐Sialylation by Virtue of Fixed Dipole Effects ofN‐Phthalyl Group: Application to Continuous Flow Synthesis of α(2‐3)‐and α(2‐6)‐Neu5Ac‐Gal Motifs by Microreactor

  摘要：

  Highly alpha-selective sialylation of sialic acid N-phenyltrifluoroacetimidate with various galactose and lactose acceptors has been achieved by introducing the C-5 N-phthalyl group on the donor. The "fixed dipole effect" of the N-phthalyl group was proposed to explain the high reactivity and a-selectivity. The microfluidic system was applied to the present alpha-sialylation, which is amenable to large-scale synthesis. The N-phthalyl group was removed by treatment with methylhydrazine acetate, for which protocol can be readily applied to the synthesis of a variety of sialic acid-containing oligosaccharides.[GRAPHICS]

  DOI：

  10.1080/07328300701634796

文献信息

• Chemical Synthesis of a Complex-Type <i>N</i>-Glycan Containing a Core Fucose
  作者：Masahiro Nagasaki、Yoshiyuki Manabe、Naoya Minamoto、Katsunori Tanaka、Alba Silipo、Antonio Molinaro、Koichi Fukase

  DOI：10.1021/acs.joc.6b02106

  日期：2016.11.18

  involving acetamide groups were found to reduce the reactivity in glycosylations: the protection of NHAc as NAc2 dramatically improved the reactivity. The dodecasaccharide–asparagine framework was constructed via the (4 + 4) glycosylation and the (4 + 8) glycosylation using the tetrasaccharide donor and the tetrasaccharide–asparagine acceptor. An ether-type solvent enhanced the yields of these key glycosylations

  实现了包含N-聚糖的核心岩藻糖的化学合成。在合成的早期引入天冬酰胺，并且糖链会聚地延长。至于片段合成，我们重新研究了α-唾液酸化，β-甘露糖基化和N-糖基化，以揭示精确的温度控制对于这些糖基化至关重要。发现涉及乙酰胺基团的分子间氢键会降低糖基化反应性：NHAc作为NAc 2的保护大大提高了反应性。使用四糖供体和四糖-天冬酰胺受体，通过（4 + 4）糖基化和（4 + 8）糖基化构建十二糖-天冬酰胺框架。醚类溶剂可提高大型底物之间这些关键糖基化的收率。在十二糖完全脱保护之后，获得目标N-聚糖。
• Efficient Synthesis of a Sialic Acid α(2→3)Galactose Building Block and Its Application to the Synthesis of Ganglioside GM3
  作者：Yunpeng Liu、Xiaohong Ruan、Xiangpeng Li、Yingxia Li

  DOI：10.1021/jo800138p

  日期：2008.6.1

  with up to 73% yield and 8.4:1 stereoselectivity, was realized when 2,3,4-unprotected galactose derivatives and TBSOTf were used as acceptors and promoter, respectively. Sialylation of 2-(trimethylsilyl)ethyl 6-O-tert-butyldiphenylsilyl-β-d-galactopyranoside (3f) gave the best result, and the resultant Neu5Ac α(2→3)Gal disaccharide was successfully used in the synthesis of ganglioside GM3.

  研究了以O-乙酰化唾液酸N-苯基三氟乙酰亚氨酸酯为供体的各种半乳糖衍生物的糖基化。当分别将2,3,4-未保护的半乳糖衍生物和TBSOTf用作受体和启动子时，实现了半乳糖的高效α（2,3）唾液酸化，产率高达73％，立体选择性高达8.4：1。的2-唾液酸化（三甲基硅烷基）乙基-6- ø -叔-butyldiphenylsilyl-β-d吡喃半乳糖苷（3F），得到最好的结果，并且将所得的Neu5Acα（2→3）半乳糖二糖在神经节苷脂GM3的合成成功地用于。
• Efficient Synthesis of the Disialylated Tetrasaccharide Motif in N-Glycans through an Amide-Protection Strategy
  作者：Jiazhou Zhou、Yoshiyuki Manabe、Katsunori Tanaka、Koichi Fukase

  DOI：10.1002/asia.201600139

  日期：2016.5.6

  glycosylation of a sialylated disaccharide with a glucosaminyl donor. This synthetic route enabled the synthesis of the as‐described disialylated structure. A more‐convergent route based on the glycosylation of two sialylated disaccharides was also established to scale up the synthesis. Protection of the amide groups in the sialic acid residues significantly increased the yield of the glycosylation reaction

  已合成了在一些N-聚糖末端发现的去唾液酸化的四糖Neu5Ac（α2,3）Gal（β1,3）[Neu5Ac（α2,6）] GlcNAc（1）。化合物1通过唾液酸供体和三糖之间的α-唾液酸化反应获得，三糖是由唾液酸化的二糖与葡萄糖胺基供体的糖基化反应合成的。这种合成途径能够合成上述的二烯丙基化结构。还建立了基于两种唾液酸化二糖糖基化的更趋同途径，以扩大合成规模。唾液酸残基中酰胺基的保护显着提高了两个唾液酸化二糖之间糖基化反应的产率，因此表明唾液酸残基上氢键的存在降低了它们的反应性。
• Efficient Sialylation with Phenyltrifluoroacetimidates as Leaving Groups
  作者：Sutang Cai、Biao Yu

  DOI：10.1021/ol0353161

  日期：2003.10.1

  [GRAPHICS]Sialylation with N-phenyltrifluoroacetimidates as leaving groups and a catalytic amount of TMSOTf as promoter compares favorably with the previous protocols for direct sialylation and expand in essence the scope of the Schmidt glycosylation reaction.