methyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside | 934592-02-6

• 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-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside
• 英文别名: methyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ylopyranosylonate-(2->6)1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside；methyl (5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosyl)onate-(2→6)-1,2-3,4-diisopropyl-α-D-galactopyranoside；methyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galactopyranoside；methyl (3aR,4R,6R,7aS)-3-acetyl-2-oxo-6-[[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methoxy]-4-[(1S,2R)-1,2,3-triacetyloxypropyl]-3a,4,7,7a-tetrahydropyrano[3,4-d][1,3]oxazole-6-carboxylate
• CAS: 934592-02-6
• 化学式: C₃₁H₄₃NO₁₈
• 分子量: 717.678
• InChiKey: AAKMTUBCEXIHSO-BXBAHXBISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  50
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  216
• 氢给体数：
  0
• 氢受体数：
  18

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-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以100%的产率得到methyl 5-acetamido-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside
  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 (phenyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycerol-β-D-galactonon-2-ulopyranoside)onate 在 吡啶 、 N-碘代丁二酰亚胺 、 甲烷磺酸 、 三氟甲磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 28.0h， 生成 methyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranosylonate-(2->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranoside
  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

文献信息

• A Divergent Method to Prepare 5-Amino-, 5-<i>N</i>-Acetamido-, and 5-<i>N</i>-Glycolylsialosides
  作者：Thomas J. Boltje、Torben Heise、Floris P. J. T. Rutjes、Floris L. van Delft

  DOI：10.1002/ejoc.201300664

  日期：2013.8

  (non-human), or amine (cancer associated) functionality. Access to homogeneous sialosides with distinct substitution patterns is essential to determine structure–activity relationships. Herein, we report a divergent chemical approach to enable the synthesis of a library of specifically substituted sialosides by using a single sialic acid building block.

  唾液酸是涉及碳水化合物识别的生物过程的重要介质。唾液酸识别的主要决定因素是 N-5 取代基，它可以是 N-乙酰基（人）、N-羟乙酰（非人）或胺（癌症相关）功能。获得具有不同取代模式的均质唾液酸对于确定结构-活性关系至关重要。在此，我们报告了一种不同的化学方法，可以通过使用单个唾液酸构建块来合成特定取代的唾液酸苷库。
• Visible Light Photoredox-Catalyzed <i>O</i>-Sialylation Using Thiosialoside Donors
  作者：Yang Yu、De-Cai Xiong、Run-Ze Mao、Xin-Shan Ye

  DOI：10.1021/acs.joc.6b00999

  日期：2016.8.19

  An efficient protocol for the O-sialylation using thiosialoside donors under visible light photocatalysis was developed. Thiosialosides were activated under the irradiation with blue light in the presence of Ru(bpy)3(PF6)2 as photocatalyst, Umemoto’s reagent as CF3 radical source and Cu(OTf)2 as an additive in acetonitrile/dichloromethane at −30 °C, and the subsequent reaction with glycosyl acceptors

  开发了一种在可见光光催化下使用硫代唾液酸供体的O-唾液酸化的有效方案。在-30°C的乙腈/二氯甲烷中，在Ru（bpy）3（PF 6）2作为光催化剂，Umemoto试剂作为CF 3自由基源和Cu（OTf）2作为添加剂的存在下，在蓝光下激活硫代硫代糖苷。C和随后与糖基受体的反应通常以令人满意的α-选择性以良好至优异的产率产生所需的唾液酸内酯。
• 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。
• Donor‐Reactivity‐Controlled Sialylation Reactions
  作者：Kesatebrhan Haile Asressu、Chun‐Wei Chang、Sarah Lam、Cheng‐Chung Wang

  DOI：10.1002/ejoc.202100718

  日期：2021.8.26

  AbstractAlthough tremendous efforts have been made for the efficient preparation of sialosides, controlling the stereochemical outcome of sialylation reaction still remains one of the most challenging tasks due to the unique chemical structure of sialic acid. We developed a new strategy to statistically analyze the stereoselectivity of sialylation reactions on six types of p‐tolyl thiosialosides in NIS/TfOH system using Relative Reactivity Value (RRV) as the indicator. Analysis of the reaction mechanism showed the formation of the relatively stable glycosyl bromide and glycosyl chloride intermediates from halide‐ and triflate‐containing promotors in the absence of an acceptor. We found that the α/β‐stereoselectivity, yields, and intermediate changes were associated with their donor reactivity. These findings enable to tailor the most suitable building blocks for stereo‐controlled sialylation reactions.
• 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.