ethyl 2,3,4-tri-O-benzyl-6-O-picoloyl-1-thio-β-D-glucopyranoside | 1415590-58-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3,4-tri-O-benzyl-6-O-picoloyl-1-thio-β-D-glucopyranoside
• 英文别名: [(2R,3R,4S,5R,6S)-6-ethylsulfanyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]methyl pyridine-2-carboxylate
• CAS: 1415590-58-7
• 化学式: C₃₅H₃₇NO₆S
• 分子量: 599.748
• InChiKey: MKFIMHIMAXGHJK-LTZUXGGGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  43
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-6-O-picoloyl-1-thio-β-D-glucopyranoside 在 copper diacetate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.17h， 以99%的产率得到ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  合成中的吡啶甲酰基保护基：专注于高度化学选择性催化去除。

  摘要：

  吡啶甲酸酯（Pico）已被证明是碳水化合物化学中的通用保护基。它可以用于通过H键介导的糖苷配基传递（HAD）方法立体控制糖基化的目的。它也可以用作临时保护基团，在合成中使用的所有其他常用保护基团的存在下，可以有效地引入和化学选择性地裂解。在本文中，我们将描述一种使用廉价的铜（II）或铁（III）盐快速，催化和高度化学选择性去除甲基吡啶基的新方法。

  DOI：

  10.1039/d0ob00803f
• 作为产物：
  描述：

  2-吡啶甲酸 、 ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以87%的产率得到ethyl 2,3,4-tri-O-benzyl-6-O-picoloyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Effect of Remote Picolinyl and Picoloyl Substituents on the Stereoselectivity of Chemical Glycosylation

  摘要：

  O-Picolinyl and O-picoloyl groups at remote positions (C-3, C-4, and C-6) can mediate glycosylation reactions by providing high or even complete facial selectivity for the attack of the glycosyl acceptor. The set of data presented herein offers a strong evidence of the intermolecular H-bond tethering between the glycosyl donor and glycosyl acceptor counterparts while providing a practical new methodology for the synthesis of either 1,2-cis or 1,2-trans linkages. Challenging glycosidic linkages including alpha-gluco, beta-manno, and beta-rhamno have seen obtained with high or complete stereocontrol.

  DOI：

  10.1021/ja307355n

文献信息

• Investigation of the H-bond-mediated aglycone delivery reaction in application to the synthesis of β-glucosides
  作者：Michael P. Mannino、Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1016/j.carres.2018.09.003

  日期：2018.12

  In an attempt to refine the H-bond-mediated Aglycone Delivery (HAD) glycosylation reaction reported herein is the synthesis of β-glucosides using an ethylthio glucoside donor equipped with the remote 6-O-picoloyl substituent. Upon examining various aliphatic, aromatic, and carbohydrate acceptors, it was determined that both electronic and steric factors may greatly affect the stereoselectivity of the

  为了改进本文报道的H键介导的糖苷配基（HAD）糖基化反应，是使用配备有远程6-O-吡啶甲基取代基的乙硫基葡萄糖苷供体合成β-葡萄糖苷。在检查了各种脂族，芳族和碳水化合物受体后，确定电子和空间因素均可极大地影响与该供体的HAD反应的立体选择性。
• Synthesis of β‐Glucosides with 3‐ <i>O</i> ‐Picoloyl‐Protected Glycosyl Donors in the Presence of Excess Triflic Acid: A Mechanistic Study
  作者：Michael P. Mannino、Alexei V. Demchenko

  DOI：10.1002/chem.201905277

  日期：2020.3.2

  Our previous study showed that picoloylated donors are capable of providing excellent facial stereoselectivity through the H-bond-mediated aglycone delivery (HAD) pathway. Presented herein is a detailed mechanistic study of stereoselective glycosylation with 3-O-picoloylated glucosyl donors. While reactions of glycosyl donors equipped with the 3-O-benzoyl group are typically non-stereoselective because

  我们之前的研究表明，通过氢键介导的糖苷配基传递（HAD）途径，甲基化的供体能够提供出色的面部立体选择性。本文提供了用3-O-吡啶甲基化的葡糖基供体的立体选择性糖基化的详细机理研究。尽管带有3-O-苯甲酰基的糖基供体的反应通常是非立体选择性的，因为这些反应是通过氧杂碳鎓中间体进行的，而3-O-吡啶甲基化的供体能够通过HAD提供增强的，但有些松弛的β-立体选择性。途径。为了改进该反应，我们注意到在NIS和化学计量的TfOH存在下，糖基化具有高度的β-立体选择性。HAD途径极不可能发生，因为在这些反应条件下，皮甲酰氮被质子化。通过低温NMR研究了质子化和糖基化，并观察到了三氟甲磺酸糖基的中间体。本文致力于扩大该反应在各种底物和靶标中的应用范围。
• Synthesis of β‐Glucosides with 3‐ <i>O</i> ‐Picoloyl‐Protected Glycosyl Donors in the Presence of Excess Triflic Acid: Defining the Scope
  作者：Michael P. Mannino、Alexei V. Demchenko

  DOI：10.1002/chem.201905278

  日期：2020.3.2

  Excellent β-stereoselectivity for the glycosylation with glucosyl donors equipped with the 3-O-picoloyl (Pico) group, without the use of participating group, was achieved in the presence of NIS/excess TfOH promoter system. A complete investigation of the scope of this reaction was performed, revealing all important attributes of successful glycosylation. While altering the halogen source was tolerated

  在存在NIS /过量TfOH启动子系统的情况下，在不使用参与基团的情况下，对于配备有3-O-picoloyl（Pico）基团的葡萄糖基供体的糖基化具有出色的β-立体选择性。对该反应范围进行了全面研究，揭示了成功糖基化的所有重要属性。在容忍改变卤素源的同时，三氟甲磺酸根阴离子的取代导致立体选择性的完全丧失。经确定，Pico基团的质子化在该反应中至关重要。还发现质子化吡啶环的稳定性或程度是获得高立体选择性的另一个重要关键因素。发现受体的亲核性与所获得的立体选择性成正比，暗示了类似于SN 2的机制。
• Cooperatively Catalyzed Activation of Thioglycosides That Bypasses Intermediacy of Glycosyl Halides
  作者：Ashley Dent、Samira Escopy、Alexei V. Demchenko

  DOI：10.1002/chem.202300873

  日期：2023.8

  A new method for the activation of thioglycosides without a glycosyl halide intermediate by using a silver salt coupled with an acid additive and molecular iodine is reported. Application of the H-bond-mediated aglycone delivery (HAD) method lead to an enhanced stereocontrol.

  报道了一种无需糖基卤化物中间体、使用银盐与酸添加剂和分子碘偶联来活化硫代糖苷的新方法。氢键介导的糖苷配基递送（HAD）方法的应用增强了立体控制。
• 6-<i>O</i>-Picolinyl and 6-<i>O</i>-Picoloyl Building Blocks As Glycosyl Donors with Switchable Stereoselectivity
  作者：Abhijeet K. Kayastha、Xiao G. Jia、Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/acs.orglett.5b02110

  日期：2015.9.18

  Remote 6-O-picolinyl or 6-O-picoloyl substituents often provide high beta-selectivity due to H-bond-mediated aglycone delivery (HAD). Herein it has been demonstrated that if the nitrogen atom of the 6-O-picolinyl or picoloyl moiety is temporarily blocked by coordination to a metal center (Pd), it cannot engage in HAD-mediated beta-glycosylation. Hence, the stereoselectivity of 6-O-picolinyl/picoloyl-assisted glycosylations can be "switched" to alpha-selectivity.