ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside | 1233488-80-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside
• 英文别名: ethyl 2-O-benzyl-3,4,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside；[(2R,3R,4S,5R,6S)-3,4-dibenzoyloxy-6-ethylsulfanyl-5-phenylmethoxyoxan-2-yl]methyl benzoate
• CAS: 1233488-80-6
• 化学式: C₃₆H₃₄O₈S
• 分子量: 626.727
• InChiKey: LAEBPXVFRAWFMY-RWRPUETGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  45
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  123
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以71%的产率得到3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity

  摘要：

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.

  DOI：

  10.1021/jo2019174
• 作为产物：
  描述：

  溴甲苯 在 吡啶 、 四丁基硫酸氢铵 、 三氟乙酸 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 18.0h， 生成 ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  非对映异构纯糖基锍盐的直接合成

  摘要：

  据报道，稳定的糖基锍盐可以通过乙基硫糖苷的直接异头 S-甲基化产生。从机制上讲，该途径代表了硫代糖苷类糖苷化活化的第一步；然而，它可以进一步合成和分离准稳定的锍离子，代表了研究这些关键中间体的新方法。

  DOI：

  10.1021/ol2009818

文献信息

• Hydrogen-Bond-Mediated Aglycone Delivery (HAD): A Highly Stereoselective Synthesis of 1,2-<i>cis</i>α-<scp>D</scp>-Glucosides from Common Glycosyl Donors in the Presence of Bromine
  作者：Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1002/chem.201406589

  日期：2015.4.20

  H‐bond mediated aglycone delivery (HAD) method recently introduced by our laboratory. At first it was noticed that high α‐stereoselectivity is only obtained with S‐ethyl glycosyl donors and only in the presence of dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTST), in high dilution, and low temperature. Combining the mechanistic studies of the HAD reaction and bromine‐promoted glycosylations

  本文描述的是我们实验室最近引入的由吡啶甲酰基保护基辅助的H键介导的糖苷配基递送（HAD）方法的扩展。最初，人们注意到只有在高稀释度和低温下，仅在S-乙基糖基供体和三氟甲磺酸二甲基（甲硫基）ulf存在下，才能获得高α-立体选择性。将HAD反应的机理研究与溴促进的糖基化结合起来，可以设计出一种非常有效的方法，该方法可以对几乎所有常见的离去基团（S-苯基，S-甲苯基，S / O-亚氨酸酯）进行高度立体选择性的α-糖基化。在常规浓度和环境温度下。
• 10.1039/d4ob00679h
  作者：Damico, Alessandra、Shrestha, Ganesh、Das, Anupama、Stine, Keith J.、Demchenko, Alexei V.

  DOI：10.1039/d4ob00679h

  日期：——

  to the development of novel classes of leaving groups based on O- and S-imidates. The main focus of the study presented herein is the synthesis of novel 3,3-difluoro-3H-indol-2-ylthio (SFox) imidates and their application as glycosyl donors in chemical glycosylation. Being thioimidates, these compounds are more stable than O-imidates albeit much more reactive than conventional alkyl/arylthio glycosides

  本文描述的是我们研究的延续，致力于开发基于 O- 和 S-imidate 的新型离开群。本文研究的主要重点是新型 3,3-二氟-3H-吲哚-2-基硫代 （SFox） 亚胺酸盐的合成及其在化学糖基化中作为糖基供体的应用。作为硫酰亚胺酸盐，这些化合物比 O-亚胺酸盐更稳定，尽管比传统的烷基/芳硫代糖苷反应性强得多。本研究表明，SFox 亚胺酸盐可以用软亲硫试剂（N-碘琥珀酰亚胺或过渡金属盐）活化，通常用于活化巯代糖苷或硫亚胺酸盐，也可以用硬亲电试剂（质子酸或路易斯酸）活化 O-亚胺酸盐。预期，从配备 2-O-苯甲酰基的 SFox 供体中获得完全的 β 选择性。令人惊讶的是，在所有研究的病例中，2-O-苄基化的 SFox 亚胺酸盐都获得了完全的 α 选择性。
• Comparison of the Armed/Disarmed Building Blocks of the <scp>d</scp>-Gluco and <scp>d</scp>-Glucosamino Series in the Context of Chemoselective Oligosaccharide Synthesis
  作者：Teerada Kamkhachorn、Archana R. Parameswar、Alexei V. Demchenko

  DOI：10.1021/ol101089u

  日期：2010.7.2

  A very elegant Fraser-Reid armed-disarmed approach recently expanded to the building blocks of the superarmed and superdisarmed series shows very high utility in chemoselective oligosaccharide synthesis. Although a number of studies dedicated to the chemoselective activation of 2-amino-2-deoxysugars have emerged, little remains known about how the reactivity of the armed/disarmed building blocks of the neutral sugars directly compares to that of their 2-aminosugar counterparts. A preliminary study of this comparative reactivity is presented.
• Direct Synthesis of Diastereomerically Pure Glycosyl Sulfonium Salts
  作者：Laurel K. Mydock、Medha N. Kamat、Alexei V. Demchenko

  DOI：10.1021/ol2009818

  日期：2011.6.3

  glycosyl sulfonium salts can be generated via direct anomeric S-methylation of ethylthioglycosides. Mechanistically, this pathway represents the first step in the activation of thioglycosides for glycosidation; however, it can further allow for the synthesis and isolation of quasi-stable sulfonium ions, representing a new approach for studying these key intermediates.

  据报道，稳定的糖基锍盐可以通过乙基硫糖苷的直接异头 S-甲基化产生。从机制上讲，该途径代表了硫代糖苷类糖苷化活化的第一步；然而，它可以进一步合成和分离准稳定的锍离子，代表了研究这些关键中间体的新方法。
• Glycosidation of Thioglycosides in the Presence of Bromine: Mechanism, Reactivity, and Stereoselectivity
  作者：Sophon Kaeothip、Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/jo2019174

  日期：2012.1.6

  Elaborating on previous studies by Lemieux for highly reactive "armed" bromides, we discovered that beta-bromide of the superdisarmed (2-O-benzyl-3,4,6-tri-O-benzoyl) series can be directly obtained from the thioglycoside precursor. When this bromide is glycosidated, alpha-glycosides form exclusively; however, the yields of such transformations may be low due to the competing anomerization into alpha-bromide that is totally unreactive under the established reaction conditions.