2-azido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranosyl trichloroacetimidate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: 2-azido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranosyl trichloroacetimidate
• 化学式: C₂₂H₂₁Cl₃N₄O₅
• 分子量: 527.792
• InChiKey: DKCFPXUOXFLHPU-BZIXAJQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.45
• 重原子数：
  34.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  118.76
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  甲醇 、 2-azido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到(2R,4aR,6R,7R,8R,8aS)-7-Azido-8-benzyloxy-6-methoxy-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  自动化的羟基反应性定量：糖基化反应的预测

  摘要：

  糖基化反应的立体选择性和产率至关重要，但不可预测。我们已经开发了一个亲核亲核常数（Aka）数据库，用于量化受空间，电子和结构效应影响的糖基化中羟基的亲核性，从而在实验和计算机算法之间建立联系。各种碳水化合物分子上的羟基之间的细微反应性差异可以由Aka定义，Aka可以通过简单便捷的自动化系统轻松访问，以确保高重现性和准确性。通过设计的软件程序“ GlycoComputer”可以组织和处理各种具有明确反应性和启动子的糖基化供体和受体，从而无需复杂的计算过程即可预测糖基化反应。通过随机森林算法进一步验证了Aka的重要性，并通过合成Lewis A骨架测试了适用性，表明可以准确估计立体选择性和产率。

  DOI：

  10.1002/anie.202013909
• 作为产物：
  描述：

  、 三氯乙腈 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 以78%的产率得到2-azido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of a β-GlcN-(1→4)-MurNAc building block en route to N-deacetylated peptidoglycan fragments

  摘要：

  Some bacteria present a variation in their peptidoglycan structure that is the absence of the N-acetyl substituent in the glucosamine residue. Very recently, this structural modification was demonstrated to be critical for host innate immune evasion in Listeria monocytogenes. To shed light on the molecular details of the evasion mechanism, the synthesis of some N-deacetylated peptidoglycan fragments is needed. En route to this goal a high-yielding synthesis of a GlcN-MurNAc disaccharide building block has been accomplished. A careful study of the optimal protecting groups and reaction conditions was done to have a complete beta-stereoselectivity in glycosylation as well as to ensure a high versatility to the disaccharide building block. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2009.12.124

文献信息

• A Study on the Influence of the Structure of the Glycosyl Acceptors on the Stereochemistry of the Glycosylation Reactions with 2-Azido-2-Deoxy-Hexopyranosyl Trichloroacetimidates
  作者：M. Belén Cid、Francisco Alfonso、Manuel Martín-Lomas

  DOI：10.1002/chem.200400746

  日期：2005.1.21

  relative influence of these factors is difficult to evaluate. For a given set of experimental conditions, the stereochemical course of these glycosylations depends on structural features of both glycosyl donor and glycosyl acceptor. It is a balance of these factors, where the structure of the glycosyl donor always plays a major role, which determines the stereochemistry of the coupling reaction. Therefore

  通过使用一系列手性肌醇衍生物作为糖基受体，研究了以2-叠氮基-2-脱氧-D-葡萄糖-和D-吡喃半乳糖基三氯乙酰亚氨酸酯作为糖基供体的糖基化的立体化学结果。糖基受体的绝对构型，构象和构象柔韧性的影响已通过在相似的预先建立的实验条件下使用不同的糖基供体进行了研究。尽管受体的结构可能在支配这些糖基化的立体化学中起一定作用，但结果表明，总的来说，这些因素的相对影响难以评估。对于给定的一组实验条件，这些糖基化的立体化学过程取决于糖基供体和糖基受体的结构特征。这些因素之间的平衡是糖基供体的结构始终起主要作用的地方，它决定了偶联反应的立体化学。因此，文献中报道的其中糖基受体的结构对于确定反应的立体化学至关重要的实施例构成了特别有利的情况，目前尚无进一步的概括。
• WO2006/129075
  申请人：——

  公开号：——

  公开（公告）日：——
• Glycosylation with Trichloroacetimidates in Ionic Liquids:  Influence of the Reaction Medium on the Stereochemical Outcome
  作者：Anna Rencurosi、Luigi Lay、Giovanni Russo、Enrico Caneva、Laura Poletti

  DOI：10.1021/jo050704x

  日期：2005.9.1

  [GRAPHICS]The glycosylation with trichloroacetimidates derived from different glycopyranoses bearing a nonparticipating group at C-2 was explored in different ionic liquids as solvents. The stereoselectivity of the reaction was significantly affected by the reaction media and by the anomeric configuration of the donor.
• Automated Quantification of Hydroxyl Reactivities: Prediction of Glycosylation Reactions
  作者：Chun‐Wei Chang、Mei‐Huei Lin、Chieh‐Kai Chan、Kuan‐Yu Su、Chia‐Hui Wu、Wei‐Chih Lo、Sarah Lam、Yu‐Ting Cheng、Pin‐Hsuan Liao、Chi‐Huey Wong、Cheng‐Chung Wang

  DOI：10.1002/anie.202013909

  日期：2021.5.25

  (Aka) to quantify the nucleophilicity of hydroxyl groups in glycosylation influenced by the steric, electronic and structural effects, providing a connection between experiments and computer algorithms. The subtle reactivity differences among the hydroxyl groups on various carbohydrate molecules can be defined by Aka, which is easily accessible by a simple and convenient automation system to assure

  糖基化反应的立体选择性和产率至关重要，但不可预测。我们已经开发了一个亲核亲核常数（Aka）数据库，用于量化受空间，电子和结构效应影响的糖基化中羟基的亲核性，从而在实验和计算机算法之间建立联系。各种碳水化合物分子上的羟基之间的细微反应性差异可以由Aka定义，Aka可以通过简单便捷的自动化系统轻松访问，以确保高重现性和准确性。通过设计的软件程序“ GlycoComputer”可以组织和处理各种具有明确反应性和启动子的糖基化供体和受体，从而无需复杂的计算过程即可预测糖基化反应。通过随机森林算法进一步验证了Aka的重要性，并通过合成Lewis A骨架测试了适用性，表明可以准确估计立体选择性和产率。
• Synthesis of a β-GlcN-(1→4)-MurNAc building block en route to N-deacetylated peptidoglycan fragments
  作者：Luigi Cirillo、Emiliano Bedini、Antonio Molinaro、Michelangelo Parrilli

  DOI：10.1016/j.tetlet.2009.12.124

  日期：2010.2

  Some bacteria present a variation in their peptidoglycan structure that is the absence of the N-acetyl substituent in the glucosamine residue. Very recently, this structural modification was demonstrated to be critical for host innate immune evasion in Listeria monocytogenes. To shed light on the molecular details of the evasion mechanism, the synthesis of some N-deacetylated peptidoglycan fragments is needed. En route to this goal a high-yielding synthesis of a GlcN-MurNAc disaccharide building block has been accomplished. A careful study of the optimal protecting groups and reaction conditions was done to have a complete beta-stereoselectivity in glycosylation as well as to ensure a high versatility to the disaccharide building block. (C) 2009 Elsevier Ltd. All rights reserved.