methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate | 934592-14-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate
• 英文别名: methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ylopyranosid)onate；methyl (3aR,4R,6R,7aS)-3-acetyl-6-octoxy-2-oxo-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydropyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 934592-14-0
• 化学式: C₂₇H₄₁NO₁₃
• 分子量: 587.621
• InChiKey: FEAPVSNDDDUXNP-SADCBOECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  41
• 可旋转键数：
  19
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  170
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以100%的产率得到methyl (octyl 5-acetamido-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate
  参考文献：
  名称：

  在二氯甲烷中用 N-乙酰基-5-N,4-O-羰基保护的硫唾液酸苷供体进行 O-唾液酸化：轻松选择性地裂解恶唑烷酮环

  摘要：

  制备了N-乙酰基-5- N , 4 - O-羰基保护的硫唾液酸苷供体，其结构已通过 X 射线晶体学确定，并在与各种受体的偶联中进行了测试。该供体在N-碘代琥珀酰亚胺和三氟甲磺酸原位活化方法（-40 °C 在二氯甲烷中）下与各种伯烷基和碳水化合物受体连接时具有优异的产率和 α-选择性。通过与N , N-二乙酰唾液酸供体的比较研究说明了恶唑烷酮子结构对 α-唾液酸化的有利影响，该供体表现出较差的产率和 α-选择性。唾液酸化选择性与供体的异头构型无关，但与NIS/TfOH活化方法下的反应温度高度相关。与 NIS/TfOH 方法相反，Ph 2 SO/Tf 2 O 促进在二氯甲烷中产生β-选择性偶联。N-乙酰基-5- N ,4- O-羰基保护的唾液酸苷（α-和β-端基异构体）的恶唑烷酮可以通过在温和条件下用甲醇钠处理而干净地裂解，而无需去除乙酰胺。

  DOI：

  10.1021/jo062431r
• 作为产物：
  描述：

  methyl S-4-methylphenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate 在 吡啶 、 N-碘代丁二酰亚胺 、 甲烷磺酸 、 乙酸酐 、 碳酸氢钠 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 1.5h， 生成 methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate
  参考文献：
  名称：

  Comparative studies on the O-sialylation with four different α/β-oriented (N-acetyl)-5-N,4-O-carbonyl-protected p-toluenethiosialosides as donors

  摘要：

  Four types of 5-N,4-O-carbonyl-protected p-toluenethiosialosides were synthesized and their couplings with different acceptors were thoroughly investigated. The results indicate that the sialyl donor structure, the amount of glycosyl acceptor, and the detailed promotion conditions have great influence on the sialylation stereoselectivties and product yields. Under the (p-Tol)(2)SO/Tf2O activation conditions, the glycosylations with simple alcohols provided declined alpha-selectivities and higher yields with increasing the amounts of acceptors from 1.1 equiv to 2.0 equiv. However, the outcome of same sialylation was independent of the relative amounts of sugar alcohol acceptors. With NIS/TfOH as promoter, the alpha-selectivities of the sialylations were significantly improved compared with the cases activated by (p-Tol)(2)SO/Tf2O. In general, the difference in configuration of N-acetylated sialyl donors (D2 and D4) has little effect on the sialylation yield and stereoselectivity. In contrast, the N-deacetylated alpha/beta sialyl donors (D1 and D3) show complex sialylation profiles with different acceptors. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2014.02.006

文献信息

• α-Selective Sialylations with N-Acetyl-5-N,4-O-Oxazolidinone-Protected p-Toluenethiosialoside
  作者：Guo-wen Xing、Fen-fen Liang、Li Chen

  DOI：10.1055/s-0028-1087539

  日期：2009.2

  A novel N-acetyl-5-N,4-O-oxazolidinone-protected p-toluenethiosialoside was readily prepared from sialic acid and p-toluenethiol. It was demonstrated that the p-toluenethiosialoside could be successfully applied to the α-selective sialylations with various glycosyl acceptors in good yields. In the coupling of N-acetyl-5-N,4-O-oxazolidinone-protected p-toluenethiosialoside and gluco alcohol, a quantitative reaction yield and high α-selectivity were obtained in dichloromethane-acetonitrile (2:1) at -40 ˚C.

  一种新型的N-乙酰-5-N,4-O-氧杂环丁烷酮保护的对甲苯硫糖苷可以方便地由唾液酸和对甲苯硫醇制备。研究表明，该对甲苯硫糖苷可以成功用于与各种糖苷受体的α-选择性唾液酸化反应，且产率良好。在N-乙酰-5-N,4-O-氧杂环丁烷酮保护的对甲苯硫糖苷与葡萄糖醇的偶联反应中，在-40°C的二氯甲烷-乙腈（2:1）中获得了定量的反应产率和高α-选择性。
• Influence of Side Chain Conformation and Configuration on Glycosyl Donor Reactivity and Selectivity as Illustrated by Sialic Acid Donors Epimeric at the 7-Position
  作者：Pavan K. Kancharla、David Crich

  DOI：10.1021/ja410683y

  日期：2013.12.18

  selectivity is also attributed to the side conformation, which in the unnatural 7R-series is placed perpendicularly above the α-face of the donor and so shields it to a greater extent than in the 7S-series. These observations are consistent with earlier conclusions on the influence of the side chain conformation on reactivity and selectivity derived from conformationally locked models in the glucose and galactose

  合成了两个 N-乙酰基 4O,5N-恶唑烷酮保护的 7 位唾液酸硫糖苷差向异构体，并比较了它们在糖基化反应中的反应性和立体选择性。结果表明，天然 7S 供体比非天然 7R 异构体更具反应性和 α 选择性。反应性的差异归因于侧链构象，特别是 O7 与异头中心的接近程度。在天然 7S 异构体中，O7 比在其非天然 7R 差向异构体中更靠近异头异构体中心，因此能够更好地支持反应位点处的初始正电荷。选择性的差异也归因于侧构象，在非自然的 7R 系列中，它垂直放置在供体的 α 面上方，因此比 7S 系列更大程度地屏蔽它。这些观察结果与从葡萄糖和半乳糖系列中的构象锁定模型得出的侧链构象对反应性和选择性影响的早期结论一致，并证实了这些影响主要是立体电子而不是扭转的建议。讨论了侧链构象作为远程保护基团影响糖基化立体选择性的一个因素以及作为糖苷键形成和水解酶促过程中的控制元素的可能相关性。对唾液酸糖苷中异头
• α-Selective Sialylations at −78 °C in Nitrile Solvents with a 1-Adamantanyl Thiosialoside
  作者：David Crich、Wenju Li

  DOI：10.1021/jo7012912

  日期：2007.9.1

  [GRAPHICS]Novel 1-adamantanylthio sialosides were synthesized and coupled to acceptors under NIS/TfOH promotion conditions. These donors showed higher reactivity than the phenylthio sialosides and could be activated by NIS/TfOH in nitrile solvents at -78 degrees C to afford improved alpha-sialylations. With the N-acetyl-5-N,4-O-oxazolidinone-protected 1-adamantanylthio sialyl donor high alpha-selectivities could be achieved in the sialylations of both primary and sterically hindered secondary acceptors, including the important galactose 3-OH acceptors.