(methyl 5-azido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate)-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galactopyranoside | 1415252-02-6

• 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 5-azido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate)-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galactopyranoside
• 英文别名: methyl 4,7,8,9-tetra-O-acetyl-5-azido-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galacotopyranoside
• CAS: 1415252-02-6
• 化学式: C₃₀H₄₃N₃O₁₇
• 分子量: 717.681
• InChiKey: LYURWTGSCOHGRI-UDLAQSOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.09
• 重原子数：
  50.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  244.87
• 氢给体数：
  0.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  (methyl 5-azido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate)-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galactopyranoside 、 S-(9-fluorenylmethyl)benzyloxythioacetate 在 吡啶 作用下， 反应 24.0h， 以47%的产率得到(methyl 5-benzyoxyacetamindo-4,7,8,9-tetra-O-acetyl-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：

  1-Picolinyl-5-azido Thiosialosides：用于唾液酸键的立体选择性构建的多功能供体。

  摘要：

  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，

  DOI：

  10.1002/anie.201909177
• 作为产物：
  描述：

  双丙酮半乳糖 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 copper diacetate 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 (methyl 5-azido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-non-2-ulopyranosylonate)-(2→6)-1,2;3,4-di-O-isopropylidene-α-D-galactopyranoside
  参考文献：
  名称：

  1-Picolinyl-5-azido Thiosialosides：用于唾液酸键的立体选择性构建的多功能供体。

  摘要：

  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，

  DOI：

  10.1002/anie.201909177

文献信息

• 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.
• Studies on the sialylation of galactoses with different C-5 modified sialyl donors
  作者：Jianzhi Gong、Han Liu、John M. Nicholls、Xuechen Li

  DOI：10.1016/j.carres.2012.08.007

  日期：2012.11

  Synthetic sialylated glycans provide useful tools to study carbohydrate-mediated biological recognition; however chemical sialylation is the most challenging practice in preparative carbohydrate chemistry, which is often associated with low yields and poor stereoselectivity. Herein, we conducted extensive studies on sialylation with five types of 5-N-modified sialyl donors and four types of galactosyl acceptors. Our studies have shown that a good combination between the donor and the acceptor seems necessary to achieve high yield and stereoselectivity. None of the donors or acceptors showed 'universal' utility toward the sialylation reaction. (C) 2012 Elsevier Ltd. All rights reserved.