methyl (4,7,8,9-tetra-O-acetyl-5-(N-acetyl)acetamido-3,5-dideoxy-β-D-glycero-D-galactonon-2-ulopyranosyl chloride)onate | 1227673-26-8

• 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 (4,7,8,9-tetra-O-acetyl-5-(N-acetyl)acetamido-3,5-dideoxy-β-D-glycero-D-galactonon-2-ulopyranosyl chloride)onate
• 英文别名: methyl 4,7,8-tetra-O-acetyl-5-(N-acetylacetamido)-2-chloro-2,3,5-trideoxy-D-glycero-β-D-galacto-2-nonulopyranosonate；methyl 4,7,8,9-tetra-O-acetyl-2-chloro-5-(N,N-diacetylamino)-2,3,5-trideoxy-β-D-glycero-D-galacto-non-2-ulo-pyranosonate
• CAS: 1227673-26-8
• 化学式: C₂₂H₃₀ClNO₁₃
• 分子量: 551.932
• InChiKey: MDLOXANLVVAKBX-QDRUEPRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.01
• 重原子数：
  37.0
• 可旋转键数：
  9.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  178.11
• 氢给体数：
  0.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  methyl (4,7,8,9-tetra-O-acetyl-5-(N-acetyl)acetamido-3,5-dideoxy-β-D-glycero-D-galactonon-2-ulopyranosyl chloride)onate 在 sodium azide 、 Bu₄NHSO₄ 、 碳酸氢钠 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 0.5h， 以82%的产率得到methyl 4,7,8,9-tetra-O-acetyl-2-azido-5-(N,N-diacetylamino)-2,3,5-trideoxy-α-D-glycero-D-galacto-non-2-ulopyranosonate
  参考文献：
  名称：

  N，N-二乙酰基唾液酸氯-一种新型的易于接近的唾液酸供体，在不存在启动子的情况下与中性和带电亲核试剂反应。

  摘要：

  首次制备N，N-二乙酰神经氨酸糖基氯，使其与各种亲核试剂反应，得到相应的α-糖基磷酸酯，β-糖基二苄基磷酸酯，α-糖基叠氮化物，α-苯基硫代糖苷和α-糖基黄药酸酯以65-82％的收率和高的立体选择性，而其与简单醇的反应不是立体选择性的。新的唾液酸供体使得首次立体选择性合成具有α-构型的唾液酸糖基磷酸酯和高效合成β-构型的唾液酸糖基磷酸二苄酯成为可能。

  DOI：

  10.1016/j.carres.2010.01.005
• 作为产物：
  描述：

  Methyl 2,4,7,8,9-penta-O-acetyl-5-(N-acetylacetamido)-3,5-dideoxy-D-glycero-α,β-D-galacto-non-2-ulopyranosonate 在 甲醇 、 乙酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到methyl (4,7,8,9-tetra-O-acetyl-5-(N-acetyl)acetamido-3,5-dideoxy-β-D-glycero-D-galactonon-2-ulopyranosyl chloride)onate
  参考文献：
  名称：

  N，N-二乙酰基唾液酸氯-一种新型的易于接近的唾液酸供体，在不存在启动子的情况下与中性和带电亲核试剂反应。

  摘要：

  首次制备N，N-二乙酰神经氨酸糖基氯，使其与各种亲核试剂反应，得到相应的α-糖基磷酸酯，β-糖基二苄基磷酸酯，α-糖基叠氮化物，α-苯基硫代糖苷和α-糖基黄药酸酯以65-82％的收率和高的立体选择性，而其与简单醇的反应不是立体选择性的。新的唾液酸供体使得首次立体选择性合成具有α-构型的唾液酸糖基磷酸酯和高效合成β-构型的唾液酸糖基磷酸二苄酯成为可能。

  DOI：

  10.1016/j.carres.2010.01.005

文献信息

• A Highly Efficient Glycosidation of Glycosyl Chlorides by Using Cooperative Silver(I) Oxide–Triflic Acid Catalysis
  作者：Scott A. Geringer、Yashapal Singh、Daniel J. Hoard、Alexei V. Demchenko

  DOI：10.1002/chem.201905576

  日期：2020.6.26

  Following our discovery that silver(I) oxide‐promoted glycosylation with glycosyl bromides can be greatly accelerated in the presence of catalytic TMSOTf or TfOH, we report herein a new discovery that glycosyl chlorides are even more effective glycosyl donors under these reaction conditions. The developed reaction conditions work well with a variety of glycosyl chlorides. Both benzoylated and benzylated

  我们发现在催化TMSOTf或TfOH的存在下，氧化银（I）促进的糖基溴化物的糖基化作用可以大大加速，我们在此报告了一个新发现，即在这些反应条件下糖基氯化物是更有效的糖基供体。发达的反应条件适用于各种糖基氯化物。苯甲酰化氯和苄基化氯化物均已成功糖基化，这些反应条件被证明对偶联含有氮和硫原子的底物有效。这种糖基化的另一个便利特征是可以直观地监测反应的进程。它的完成可以通过Ag 2 O特有的深色消失来判断。
• Differences in reactivity of N-acetyl- and N,N-diacetylsialyl chlorides caused by their different supramolecular organization in solutions
  作者：A. V. Orlova、T. V. Laptinskaya、N. V. Bovin、L. O. Kononov

  DOI：10.1007/s11172-017-1999-x

  日期：2017.11

  O-Sialylation of a substituted indolin-3-one under phase-transfer catalysis conditions, which does not occur when N-acetylsialyl chloride is used, proceeds with N,N-diacetylsialyl chloride as the glycosyl donor. A study using dynamic light scattering of solutions of both sialyl chlorides under conditions close to the conditions used for glycosylation showed a difference in the correlation radii of light scattering

  在相转移催化条件下取代 indolin-3-one 的 O-唾液酸化，在使用 N-乙酰唾液酸氯时不会发生，以 N,N-二乙酰唾液酸氯作为糖基供体进行。在接近糖基化条件的条件下使用两种唾液酰氯溶液的动态光散射的研究表明，此类溶液中光散射粒子的相关半径存在差异。这表明将额外的 N-乙酰基引入唾液酰氯显着改变了糖基供体的超聚体的结构，这显然增加了单个分子对亲核试剂攻击的可及性，从而增加了其反应性。
• Black Swan in Phase Transfer Catalysis: Influence of Mixing Mode on the Stereoselectivity of Glycosylation
  作者：Ilya V. Myachin、Zarina Z. Mamirgova、Elena V. Stepanova、Alexander I. Zinin、Alexander O. Chizhov、Leonid O. Kononov

  DOI：10.1002/ejoc.202101377

  日期：2022.4.12

  The influence of mixing mode on the outcome of the glycosylation under phase transfer conditions (batch vs flow) is found to be more complicated than it is generally assumed. A change in the way reagents are mixed leads not only to the enhanced mass transfer and consequently higher yield but also to a change in reaction mechanism.

  发现混合模式对相转移条件（批次与流动）下糖基化结果的影响比通常假设的要复杂。试剂混合方式的改变不仅导致增强的传质和因此更高的产率，而且导致反应机制的改变。
• 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.