ethyl 3-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
• 英文别名: [(2R,4aR,6S,7R,8R,8aR)-6-ethylsulfanyl-7-hydroxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate
• 化学式: C₂₂H₂₄O₆S
• 分子量: 416.495
• InChiKey: ZGKCVSIIAKOJAL-ZQMBKUMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  99.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside 在 4-二甲氨基吡啶 、 18-冠醚-6 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.5h， 生成 benzoxazolyl 3-O-benzoyl-4,6-O-benzylidene-2-O-levulinoyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of oligosaccharide fragments of capsular polysaccharide Staphylococcus aureus type 8

  摘要：

  To enhance our understanding of the activation and conjugation processes, reported herein is the synthesis of oligosaccharides comprising two sequential repeating units of capsular polysaccharideS. aureusserotype 8 (CP8). As in our previous syntheses of staphylococcal oligosaccharides, the potential propagation positions are blocked with methyl groups. While protein conjugates of carbohydrate antigens based on the structure of theS. aureuscapsular serotypes have the potential to contribute to aS. aureusvaccine, despite promising preclinical data, efficacy has not been detected in human populations thus far.

  DOI：

  10.1080/07328303.2020.1821042
• 作为产物：
  描述：

  苯甲酰氯 、 ethyl 4,6-O-benzylidene-1-thio-β-D-glucopyranoside 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 25.17h， 以48%的产率得到ethyl 3-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Regioselective C-3-O-acylation and O-alkylation of 4,6-O-benzylidene-β-d-glucopyranoside, derivatives displaying a range of anomeric substituents

  摘要：

  Regioselective C-3-O-acylation and O-alkylation of ethyl 4,6-O-benzylidene-1-thio-beta-D-glucopyranoside, phenyl 4,6-O-benzylidene-beta-D-glucopyranoside and phenyl 4,6-O-benzylidene-1-seleno-beta-D-glucopyranoside is described. Regioselectivity is obtained by first treating the benzylidene diols with sodium hydride and copper (II) chloride to form a THF soluble copper chelate. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01420-3

文献信息

• 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。
• Garegg, Per J.; Kvarnstroem, Ingemar; Niklasson, Annika, Journal of Carbohydrate Chemistry, 1993, vol. 12, # 7, p. 933 - 954
  作者：Garegg, Per J.、Kvarnstroem, Ingemar、Niklasson, Annika、Niklasson, Gunilla、Svensson, Stefan C. T.

  DOI：——

  日期：——
• Regioselective C-3-O-acylation and O-methylation of 4,6-O-benzylidene-β-d-gluco- and galactopyranosides displaying a range of anomeric substituents
  作者：Helen M.I Osborn、Victoria A Brome、Laurence M Harwood、William G Suthers

  DOI：10.1016/s0008-6215(01)00063-5

  日期：2001.5

  The regioselective C-3-O-acylation and O-methylation of a range of 4,6-O-benzylidene-beta -D-gluco- and galactopyranosides has been studied. Regioselectivity is achieved by forming the copper chelate of the 2,3-diol using either sodium hydride and copper(II) chloride, or copper(II) acetylacetanoate, or copper(II) acetate, prior to introduction of the acylating or methylating agent. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Synthesis of oligosaccharide fragments of capsular polysaccharide <i>Staphylococcus aureus</i> type 8
  作者：Satsawat Visansirikul、Stephen A. Kolodziej、Alexei V. Demchenko

  DOI：10.1080/07328303.2020.1821042

  日期：2020.9.1

  To enhance our understanding of the activation and conjugation processes, reported herein is the synthesis of oligosaccharides comprising two sequential repeating units of capsular polysaccharideS. aureusserotype 8 (CP8). As in our previous syntheses of staphylococcal oligosaccharides, the potential propagation positions are blocked with methyl groups. While protein conjugates of carbohydrate antigens based on the structure of theS. aureuscapsular serotypes have the potential to contribute to aS. aureusvaccine, despite promising preclinical data, efficacy has not been detected in human populations thus far.
• Regioselective C-3-O-acylation and O-alkylation of 4,6-O-benzylidene-β-d-glucopyranoside, derivatives displaying a range of anomeric substituents
  作者：Jonathan J. Gridley、Helen M.I. Osborn、William G. Suthers

  DOI：10.1016/s0040-4039(99)01420-3

  日期：1999.9

  Regioselective C-3-O-acylation and O-alkylation of ethyl 4,6-O-benzylidene-1-thio-beta-D-glucopyranoside, phenyl 4,6-O-benzylidene-beta-D-glucopyranoside and phenyl 4,6-O-benzylidene-1-seleno-beta-D-glucopyranoside is described. Regioselectivity is obtained by first treating the benzylidene diols with sodium hydride and copper (II) chloride to form a THF soluble copper chelate. (C) 1999 Elsevier Science Ltd. All rights reserved.