methyl S-4-methylphenyl 5-azido-4,7,8,9-tetra-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate | 374573-39-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl S-4-methylphenyl 5-azido-4,7,8,9-tetra-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate
• 英文别名: methyl (tolyl 5-azido-4,7,8,9-tetra-O-acetyl-3,5-di-deoxy-2-thio-D-glycero-α-D-galacto-non-2-ulopyranoside)onate；methyl p-tolyl 4,7,8,9-tetra-O-acetyl-5-azido-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosonate；methyl (2S,4S,5R,6R)-4-acetyloxy-5-azido-2-(4-methylphenyl)sulfanyl-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 374573-39-4
• 化学式: C₂₅H₃₁N₃O₁₁S
• 分子量: 581.601
• InChiKey: UOWJKRWRQMRTKZ-AWJATLGSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  40
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  180
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  methyl S-4-methylphenyl 5-azido-4,7,8,9-tetra-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate 在 N-溴代丁二酰亚胺(NBS) 、 水 、 N,N-二异丙基乙胺 作用下， 以 丙酮 、 乙腈 为溶剂， 反应 1.5h， 生成 methyl (2R,4S,5R,6R)-4-acetyloxy-5-azido-2-diethoxyphosphanyloxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
  参考文献：
  名称：

  The Thioglycoside and Glycosyl Phosphite of 5-Azido Sialic Acid: Excellent Donors for theα-Glycosylation of Primary Hydroxy Groups

  摘要：

  5-Azido sialyl donors with O-acetyl protecting groups are useful α-selective glycosylation reagents, especially for primary hydroxyl groups as acceptors. This is shown with a variety of reactions using 1 as a sialyl donor. It was also possible to synthesize NeuAcα(2→9)NeuAc as a thioglycoside donor for use in subsequent glycosylations.

  DOI：

  10.1002/1521-3773(20010803)40:15<2900::aid-anie2900>3.0.co;2-4
• 作为产物：
  描述：

  (2S,4S,5R,6R)-5-Amino-4-hydroxy-2-p-tolylsulfanyl-6-((1R,2R)-1,2,3-trihydroxy-propyl)-tetrahydro-pyran-2-carboxylic acid methyl ester 在 吡啶 、 triflic azide 、 copper(II) sulfate 作用下， 以 甲醇 为溶剂， 反应 27.0h， 生成 methyl S-4-methylphenyl 5-azido-4,7,8,9-tetra-3,5-dideoxy-2-thio-D-glycero-α-D-galacto-2-nonulopyranosidonate
  参考文献：
  名称：

  The Thioglycoside and Glycosyl Phosphite of 5-Azido Sialic Acid: Excellent Donors for theα-Glycosylation of Primary Hydroxy Groups

  摘要：

  5-Azido sialyl donors with O-acetyl protecting groups are useful α-selective glycosylation reagents, especially for primary hydroxyl groups as acceptors. This is shown with a variety of reactions using 1 as a sialyl donor. It was also possible to synthesize NeuAcα(2→9)NeuAc as a thioglycoside donor for use in subsequent glycosylations.

  DOI：

  10.1002/1521-3773(20010803)40:15<2900::aid-anie2900>3.0.co;2-4

文献信息

• Microbial Glycosyltransferases for Carbohydrate Synthesis:  α-2,3-Sialyltransferase from <i>Neisseria </i><i>g</i><i>onorrheae</i>
  作者：Masayuki Izumi、Gwo-Jenn Shen、Shirley Wacowich-Sgarbi、Takuji Nakatani、Oliver Plettenburg、Chi-Huey Wong

  DOI：10.1021/ja011382r

  日期：2001.11.1

  exploitation of its substrate specificity and synthetic utility. Several potential acceptor substrates were synthesized in this study, including mono- and oligosaccharides, glycolipids, and glycopeptides and their sulfate derivatives. Some CMP-sialic acid derivatives with modification at the C-5 position were also prepared for evaluation as donor substrates. It was found that the enzyme exhibits a broader

  来自淋病奈瑟菌的 α-2,3-唾液酸转移酶在大肠杆菌中过度生产，以利用其底物特异性和合成效用。本研究合成了几种潜在的受体底物，包括单糖和寡糖、糖脂、糖肽及其硫酸盐衍生物。还制备了一些在 C-5 位进行修饰的 CMP-唾液酸衍生物作为供体底物进行评估。发现与其他唾液酸转移酶相比，该酶表现出更广泛的受体底物特异性，尽管供体特异性非常有限。已证明该酶在代表性唾液酸糖缀合物的制备性合成中的应用。在这项工作和其他人的工作的基础上，
• 1‐Picolinyl‐5‐azido Thiosialosides: Versatile Donors for the Stereoselective Construction of Sialyl Linkages
  作者：Jian Chen、Thomas Hansen、Qing‐Ju Zhang、De‐Yong Liu、Yao Sun、Hao Yan、Jeroen D. C. Codée、Richard R. Schmidt、Jian‐Song Sun

  DOI：10.1002/anie.201909177

  日期：2019.11.18

  flexibility in sialoside derivative synthesis, high temperature tolerance and easy scalability. In particular, the applicability to the synthesis of complex and bioactive N-glycan antennae when combined with the MPEP glycosylation protocol via the "latent-active" strategy has been shown. Mechanistically, the excellent α-stereoselectivity of the novel sialylation protocol could be attributed to the dramatic

  以picolinyl（Pic）基团为C-1定位的导向基团，N3为C5-NH2的通用前体，设计并合成了一种新型的1-Pic-5-N3硫代唾液酸供体，在此基础上建立了新的唾液酸化方案。与传统的唾液酸化方法相比，新方案显示出明显的优势，包括在无溶剂效应的情况下具有出色的α-立体选择性，广泛的底物范围（包括具有挑战性的唾液酸受体的唾液基8和9-羟基），唾液酸衍生物的柔韧性合成，耐高温和易于扩展。特别地，已经显示出当通过“潜在活性”策略与MPEP糖基化方案结合时，对于合成复杂且具有生物活性的N-聚糖触角的合成的适用性。机械上，
• 一种I型N-聚糖天线的合成方法
  申请人：江西师范大学

  公开号：CN110016066B

  公开（公告）日：2021-11-02

  本发明公开一种I型N‑聚糖天线的合成方法，通过结合2‑糖苷化方法和MPEP糖基化的方案，I型天线可以通过最长7步线线性合成从容易获得的单糖切块获得，总收率为29％。本发明解决了唾液酸糖苷化立体选择性差和产率低的问题，高效高立体选择性的制备了I型N‑聚糖天线，大大缩短了合成路线,为大量合成提供了可能，将大大推进N‑聚糖类化合物的活性机理研究及其结构‑活性关系的研究。
• 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.