methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate | 73208-80-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate
• 英文别名: methyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosid)onate；2-α-O-methyl-4,7,8,9-tetra-O-acetyl-neuraminic acid methyl ester；methyl (methyl-5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosonid)onate；(1S,2R)-1-((2R,3R,4S,6R)-3-Acetamido-4-acetoxy-6-methoxy-6-(methoxycarbonyl)tetrahydro-2H-pyran-2-yl)propane-1,2,3-triyl triacetate；methyl (2R,4S,5R,6R)-5-acetamido-4-acetyloxy-2-methoxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 73208-80-7
• 化学式: C₂₁H₃₁NO₁₃
• 分子量: 505.476
• InChiKey: BDVAGIAWBFWKLD-YKFXCJJJSA-N

物化性质

• 熔点：
  137-139°C
• 沸点：
  593.7±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿、二氯甲烷、乙醚、乙酸乙酯、甲醇

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  35
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  179
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate 在 sodium hydroxide 、 ammonium hydroxide 作用下， 以 水 为溶剂， 反应 0.25h， 以80%的产率得到ammonium (methyl 5-amino-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosid)onate
  参考文献：
  名称：

  Microwave-assisted synthesis of N-glycolylneuraminic acid derivatives

  摘要：

  A rapid, efficient and scalable synthesis of biologically-relevant N-glycolylneuraminic acid derivatives from the natural N-acetyl (Neu5Ac) precursors has been developed. Microwave irradiation provides accelerated de-N-acetylation compared to more traditional methods, with optimised NaOH-promoted de-N-acetylation in only 15 min. The prepared amines were readily re-N-acylated to afford the corresponding N-glycolyl (Neu5Gc) analogues. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2013.07.107
• 作为产物：
  描述：

  2,4,7,8,9-Penta-O-acetyl-N-acetyl-β-D-neuraminsaeure 在 盐酸 作用下， 以 二氯甲烷 为溶剂， 反应 15.0h， 生成 methyl [methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-α-D-glycero-D-galacto-non-2-ulopyranoside]onate
  参考文献：
  名称：

  低聚物从酰胺连接的神经氨酸衍生类似物的合成＃

  摘要：

  已经制备了由α - O-甲氧基-和2，3-脱氢尿嘧啶酸衍生的N-氟人-9-基甲氧基羰基保护的糖氨基酸。将这些单体单元结合到固相合成中导致有效合成长度从一到八个单元的两个系列的低聚物。将2，3-脱氢尿嘧啶酸的（1→5）-连接的酰胺进一步进行氢化，得到在异头碳处具有β-氢取代基的第三系列低聚物。

  DOI：

  10.1021/jo035312+

文献信息

• A Highly α-Stereoselective Sialylation Method Using 4-<i>O</i> -4-Nitropicoloyl Thiosialoside Donor
  作者：Dong-Mei Liu、Hong-Ling Wang、Jin-Cai Lei、Xian-Yang Zhou、Jin-Song Yang

  DOI：10.1002/ejoc.201901587

  日期：2020.2.7

  The sialic acid ethyl thioglycoside donor, bearing a 4‐nitropicoloyl moiety as the stereodirecting group at the C4 position, can successfully achieve highly α‐sialylation with various acceptors. The method has been extended to the stereocontrolled synthesis of the protected trisaccharide found in the repeating unit of serotype Ia Group B Streptococcus capsular polysaccharide.

  唾液酸乙基硫代糖苷供体，在C4位置带有一个4 －硝基香叶基作为立体定向基团，可以成功地实现与各种受体的高度α－唾液酸化。该方法已扩展到在血清型Ia B族链球菌荚膜多糖重复单元中发现的被保护的三糖的立体控制合成。
• Syntheses of 2-O-glycosyl derivatives of N-acetyl-d-neuraminic acid
  作者：Haruo Ogura、Kimio Furuhata、Masayoshi Itoh、Yoshiyasu Shitori

  DOI：10.1016/0008-6215(86)84004-6

  日期：1986.12

  Abstract Syntheses of N -acetyl- d -neuraminic acid derivatives are reported. Methyl 4,7,8,9-tetra- O -acetyl- N -acetyl-2-chloro-2-deoxy-β- d -neuraminate ( 3 ) was prepared directly from methyl N -acetyl-β- d -neuraminate ( 2 ) in good yield. Koenigs-Knorr reaction of 3 with an excess of methanol gave the methyl α-glycoside of methyl N -acetyl- d -neuraminate ( 4 ). 2,3- O -Isopropylidene- d -ribono-1

  摘要报道了N-乙酰基-d-神经氨酸衍生物的合成。4,7,8,9-四-O-乙酰基-N-乙酰基-2-氯-2-脱氧-β-d-神经氨酸甲酯（3）直接由N-乙酰基-β-d-神经氨酸甲酯（3）直接制备2）收率好。3与过量甲醇的Koenigs-Knorr反应得到N-乙酰基-d-神经氨酸甲酯的甲基α-糖苷（4）。2，3-O-异亚丙基-d-核糖基-1,4-内酯，2,3-O-异亚丙基神经氨酸和5-氟-2,3-O-异亚丙基神经氨酸与3反应生成甲基N-乙炔基的端基异构体混合物-d-神经氨酸衍生物。这些化合物的立体化学由nmr和cd光谱以及糖苷键水解速率的测定证实。
• A synthesis of N-acetylneuraminic acid and [6-2H]-N-acetyl-neuraminic acid from N-acetyl-d-glucosamine
  作者：Radomir Julina、Ingrid Müller、Andrea Vasella、René Wyler

  DOI：10.1016/0008-6215(87)80145-3

  日期：1987.7

  diastereo-selectively in high yields. Debenzylidenation of 6 freed its distal primary carbinol group, which was subjected to catalytic oxidation followed by hydrolysis, esterification (diazomethane), and acetylation to give a protected methyl nononate. This ester was transformed into the known methyl N-acetyl-4,7,8,9-tetra-O-acetyl-2,3-dehydroneuraminate (15), which was identical with a sample prepared from Neu5Ac. Neu5Ac

  由2-乙酰氨基-2-脱氧-D-葡萄糖（N-乙酰基-D-葡萄糖胺）制备N-乙酰神经氨酸（Neu5Ac）和[6-2H] -Neu5Ac。然后GlcNAc的1-脱氧-1-硝基衍生物（被保护的1-C-硝基脱水-D-葡萄糖醇）与环己叉基-D-甘油醛进行亨利反应，然后依次进行乙酰化和Bu3SnH的还原脱硝，得到脱水壬醇中间体（6 ）以高产非对映选择性。6的脱苄基作用释放了其远端的伯甲醇基团，对其进行催化氧化，然后水解，酯化（重氮甲烷）和乙酰化，得到保护的壬酸甲酯。将该酯转化为已知的甲基N-乙酰基-4,7,8,9-四-O-乙酰基-2,3-去氢尿酸铀酸酯（15），与从Neu5Ac制备的样品相同。Neu5Ac通过溴醚化（NBS，甲醇），然后用Bu3SnH还原脱溴并水解。类似地，将15的[6-2H]衍生物转化为[6-2H] -Neu5Ac。
• Differential Recognition of Diet-Derived Neu5Gc-Neoantigens on Glycan Microarrays by Carbohydrate-Specific Pooled Human IgG and IgA Antibodies
  作者：Shani Leviatan Ben-Arye、Christoph Schneider、Hai Yu、Salam Bashir、Xi Chen、Stephan von Gunten、Vered Padler-Karavani

  DOI：10.1021/acs.bioconjchem.9b00273

  日期：2019.5.15

  Sialic acids (Sias) cover vertebrate cell surface glycans. N-Acetylneuraminic acid (Neu5Ac) and its hydroxylated form N-glycolylneuraminic acid (Neu5Gc) are common Sia in mammals. Humans cannot synthesize Neu5Gc but accumulate it on cells through red-meat rich diets, generating numerous immunogenic Neu5Gc-neoantigens. Consequently, humans have diverse anti-Neu5Gc antibodies affecting xenotransplantation, cancer, atherosclerosis, and infertility. Anti-Neu5Gc antibodies circulate as IgG, IgM, and IgA isotypes; however, repertoires of the different isotypes in a large population have not been studied yet. Here, we used glycan microarrays to investigate anti-Neu5Gc IgGs and IgAs in intravenous immunoglobulin (IVIG) or pooled human IgA, respectively. Binding patterns on microarrays fabricated with Neu5Gc- and Neu5Ac-glycans, together with inhibition assays, revealed that different IVIG preparations have highly specific anti-Neu5Gc IgG reactivity with closely related repertoires, while IgAs show cross-reactivity against several Neu5Ac-glycans. Such different anti-Neu5Gc IgG/IgA repertoires in individuals could possibly mediate distinctive effects on human diseases.

  硅烷酸（Sias）覆盖脊椎动物细胞表面的聚糖。N-乙酰神经氨酸（Neu5Ac）及其羟化形式 N-乙酰神经氨酸（Neu5Gc）是哺乳动物常见的 Sia。人类不能合成 Neu5Gc，但通过富含红色肉类的饮食将其积累在细胞上，产生了大量具有免疫原性的 Neu5Gc-新抗原。因此，人类产生了多种抗 Neu5Gc 抗体，影响了异种移植、癌症、动脉粥样硬化和不孕症。抗 Neu5Gc 抗体以 IgG、IgM 和 IgA 三种异型循环存在；然而，目前还没有对大量人群中不同异型抗体的复合物进行研究。在这里，我们使用聚糖微阵列分别研究了静脉注射免疫球蛋白（IVIG）或集合人类 IgA 中的抗 Neu5Gc IgG 和 IgA。用 Neu5Gc 和 Neu5Ac 聚糖制作的微阵列上的结合模式以及抑制测定显示，不同的 IVIG 制剂具有高度特异性的抗 Neu5Gc IgG 反应，其反应谱密切相关，而 IgA 则对几种 Neu5Ac 聚糖表现出交叉反应。个体中这种不同的抗 Neu5Gc IgG/IgA 反应谱可能会对人类疾病产生不同的影响。
• Glycosylation of 4,7,8,9-Tetra-<i>O</i>-acetyl-2-deoxy-2β,3β-epoxy-<i>N</i>-acetylneuraminic Acid Methyl Ester
  作者：Kaoru Okamoto、Tadao Kondo、Toshio Goto

  DOI：10.1246/bcsj.60.637

  日期：1987.2

  Reaction of the 2β,3β-epoxyneuraminic acid derivative prepared from 2,3-dehydroneuraminic acid derivative with primary or secondary alcohol gave the corresponding glycoside(s) or ortho ester.

  由 2,3-脱氢酮乌拉敏酸衍生物制备的 2β,3β-环氧新乌拉敏酸衍生物与伯醇或仲醇反应，可得到相应的苷或原酯。