methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-α,β-D-galacto-non-2-ulopyranoside)onate | 1219717-79-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-α,β-D-galacto-non-2-ulopyranoside)onate
• 英文别名: methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranoside)onate；dibutyl [methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosyl)onate] phosphate；Methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-alpha-D-galacto-non-2-ulopyranoside)onate；methyl (3aR,4R,6S,7aS)-3-acetyl-6-dibutoxyphosphoryloxy-2-oxo-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydropyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 1219717-79-9
• 化学式: C₂₇H₄₂NO₁₆P
• 分子量: 667.601
• InChiKey: RRUMOCNIWQTNRP-WMDHSACJSA-N

物化性质

• 沸点：
  687.6±55.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  45
• 可旋转键数：
  21
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  206
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-α,β-D-galacto-non-2-ulopyranoside)onate 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.83h， 生成 methyl 5-acetamido-2,6-anhydro-3,5-dideoxy-2-C-(2-propenyl)-D-erythro-L-gluco-nononate
  参考文献：
  名称：

  Stereoselective, Electrophilic α-C-Sialidation

  摘要：

  5-N-Acetyl-5-N,4-O-oxazolidinone protected alpha- and beta-sialyl phosphates react with allyltributylstannane and a variety of trimethylsilyl enol ethers to give alpha-sialyl C-glycosides in high yield and excellent selectivity. Elimination to give the 2,3-glycal is minimized by the presence of the oxazolidinone ring. The oxazolidinone ring can be subsequently cleaved under mild conditions at room temperature leaving in place the native acetamide group.

  DOI：

  10.1021/ol300255q
• 作为产物：
  描述：

  5-乙酰氨基-4,7,8,9-四-O-乙酰基-3,5-双脱氧-2-S-苯基-2-硫基-D- 在 甲烷磺酸 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 38.0h， 生成 methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-2-(dibutylphosphoryl)-3,5-dideoxy-D-glycero-α,β-D-galacto-non-2-ulopyranoside)onate
  参考文献：
  名称：

  Screening of Neu5Acα(2–6)gal isomer preferences of siglecs with a sialic acid microarray

  摘要：

  Neu5Acα(2–6)Gal结构类似物的合成显示出与保守的siglecs（hCD22和mCD22）相比，与快速进化的siglecs（Siglecs -3和-10）具有不同的结合模式。

  DOI：

  10.1039/c6ob01688j

文献信息

• Synthesis of an Aminooxy Derivative of the GM3 Antigen and Its Application in Oxime Ligation
  作者：Kristopher A. Kleski、Mengchao Shi、Matthew Lohman、Gabrielle T. Hymel、Vinod K. Gattoji、Peter R. Andreana

  DOI：10.1021/acs.joc.0c00320

  日期：2020.12.18

  The anomeric aminooxy GM3 trisaccharide cancer antigen (Neu5Acα2,3Galβ1,4Glcβ-ONH2) has been chemically synthesized using a linear glycosylation approach. The key step involves a highly α(2,3)-stereoselective sialylation to a galactose acceptor. The Neu5Acα2,3Gal intermediate was functionalized as a donor for a [2 + 1] glycosylation, including a glucose acceptor that featured an O-succinimidyl group

  氨氧基GM3三糖癌抗原的异头（Neu5Acα2,3Galβ1,4Glcβ-ONH 2）已经使用线性糖基化的方法化学合成。关键步骤涉及对半乳糖受体的高度α（2,3）-立体选择性唾液酸化。Neu5Acα2,3Gal中间体被功能化为[2 +1]糖基化的供体，其中包括在还原端具有O-琥珀酰亚胺基的氨基葡萄糖作为氨基氧基前体。然后将完全脱保护的异头氨基氧基GM3三糖通过肟连接缀合到免疫相关的两性离子多糖PSA1上。
• Synthesis and Evaluation of Liposomal Anti-GM3 Cancer Vaccine Candidates Covalently and Noncovalently Adjuvanted by αGalCer
  作者：Xu-Guang Yin、Jie Lu、Jian Wang、Ru-Yan Zhang、Xi-Feng Wang、Chun-Miao Liao、Xiao-Peng Liu、Zheng Liu、Jun Guo

  DOI：10.1021/acs.jmedchem.0c01186

  日期：2021.2.25

  candidates: (a) self-adjuvanting vaccine GM3-αGalCer by conjugating GM3 with αGalCer and (b) noncovalent vaccine GM3-lipid/αGalCer, in which GM3 is linked with lipid anchor and coassembled with αGalCer. This demonstrated that βGalCer is an exceptionally optimized lipid anchor, which enables the noncovalent vaccine candidate GM3-βGalCer/αGalCer to evoke a comparable antibody level to GM3-αGalCer. However

  GM3是一种典型的肿瘤相关糖抗原，被认为是癌症疫苗开发的重要靶点，但其低免疫原性限制了其应用。 αGalCer 是一种 iNKT 细胞激动剂，已通过独特的免疫模式用作佐剂。在此，我们制备并研究了两种类型的抗肿瘤候选疫苗：（a）通过将 GM3 与 αGalCer 结合而产生的自我佐剂疫苗GM3- αGalCer 和（b）非共价疫苗GM3-lipid/αGalCer ，其中 GM3 与脂质锚连接并共组装与αGalCer。这证明 βGalCer 是一种经过特别优化的脂质锚，使非共价候选疫苗GM3-βGalCer/αGalCer能够激发与GM3-αGalCer相当的抗体水平。然而， GM3-αGalCer诱导的抗体更能识别B16F10癌细胞，更有效地激活补体系统。我们的研究强调了利用 αGalCer 与碳水化合物抗原之间的共价或非共价组装来构建疫苗结构以及选择合适的脂质锚用于非共价疫苗配方的重要性。
• Highly Alpha-Selective Sialyl Phosphate Donors for Efficient Preparation of Natural Sialosides
  作者：Che-Hsiung Hsu、Kuo-Ching Chu、Yih-Shyan Lin、Jeng-Liang Han、Yu-Shiang Peng、Chien-Tai Ren、Chung-Yi Wu、Chi-Huey Wong

  DOI：10.1002/chem.200903035

  日期：2010.2.8

  Hubble, bubble, toil, and trouble: The use of a new sialyl phosphate donor allows the stereoselective, one‐pot multicomponent synthesis of α‐sialooligosaccharides (see scheme).

  哈勃，气泡，辛劳和麻烦：使用新的唾液酸磷酸酯供体可以立体选择性地单锅多组分合成α-唾液寡糖（参见方案）。
• Alpha-selective sialyl phosphate donors for preparation of sialosides and sialoside arrays for influenza virus detection
  申请人：Wong Chi-Huey

  公开号：US08507660B2

  公开（公告）日：2013-08-13

  A novel N-acetyl-5-N,4-O-carbonyl-protected dibutyl sialyl phosphate donor for sialylation of both primary and sterically hindered secondary acceptors to prepare sialosides with high yield and α-selectivity is disclosed. Methods for making disaccharide building blocks comprising α(2→3), α(2→6), α(2→8), α(2→8)/α(2→9) alternate, and α(2→9) sialosides are provided. methods for one-pot synthesis of complex sialosides are disclosed. Libraries of sialosides and methods for using the libraries for detection and receptor binding analysis of surface glycoproteins or pathogens and cancer cells are disclosed. Methods for distinguishing between hemagglutinin (HA) from various strains of influenza are provided.

  揭示了一种新型N-乙酰-5-N,4-O-羰基保护的二丁基唾液酸磷酸供体，用于唾液酸化处理一次和立体位阻次级受体，以制备产率高且α-选择性的唾液苷。提供了制备包括α(2→3)、α(2→6)、α(2→8)、α(2→8)/α(2→9)交替和α(2→9)唾液苷的二糖构建块的方法。揭示了一锅法合成复杂唾液苷的方法。还揭示了唾液苷库及其用于检测和受体结合分析表面糖蛋白或病原体和癌细胞的方法。提供了用于区分不同流感病毒株血凝素（HA）的方法。
• A Modular Chemoenzymatic Synthesis of Disialosyl Globopentaosylceramide (DSGb5Cer) Glycan
  作者：Dung-Yeh Wu、Avijit K. Adak、Yan-Ting Kuo、Yu-Ju Shen、Pei-Jhen Li、Jih Ru Hwu、Chun-Cheng Lin

  DOI：10.1021/acs.joc.0c01091

  日期：2020.12.18

  The total synthesis of the oligosaccharide moiety of disialosyl globopentaosylceramide (DSGb5 Cer), a dominant ganglioside isolated from malignant renal cell carcinoma tissues, is reported. The synthetic strategy relies on a chemical α(2,6)-sialylation at the internal GalNAc unit of a Gb5 pentasaccharide backbone that furnishes a Neu5Acα(2,6)GalNAc-linked hexasaccharide, suitable for an enzymatic α(2

  报道了从恶性肾细胞癌组织中分离出的主要神经节苷脂二唾液酸 globopentaosylceramide (DSGb5 Cer) 的寡糖部分的全合成。合成策略依赖于 Gb5 五糖骨架内部 GalNAc 单元的化学 α(2,6)-唾液酸化，提供 Neu5Acα(2,6)GalNAc 连接的六糖，适用于酶促 α(2,3)-末端 Gal 残基的唾液酸化以构建七糖聚糖。通过基于 Galβ(1,3)[Neu5Acα(2,6)]GalNAc 三糖供体和 Gb3 的 [3+3] 糖基化，也实现了对这一关键 α(2,6)-唾液酸化六糖的收敛访问受体。在还原端带有 6-叠氮己基苷元的合成 DSGb5 聚糖可以进行进一步的区域选择性功能化。