methyl 2-O-benzyl-3,4,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside | 1233488-82-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-O-benzyl-3,4,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl 2-O-benzyl-3, 4, 6-tri-O-benzoyl-D-glucopyranosyl-α-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 6-O-(3,4,6-tri-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；methyl 2,3,4-tri-O-benzyl-6-O-(2-O-benzyl-3,4,6-tri-O-benzoyl-α-D-glucopyranosyl)-α-D-glucopyranoside；methyl 6-O-(3,4,6-O-benzoyl-2-O-benzyl-α-D-glucopyranosyl)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；Bn(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Glc(a1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；[(2R,3R,4S,5R,6S)-3,4-dibenzoyloxy-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-5-phenylmethoxyoxan-2-yl]methyl benzoate
• CAS: 1233488-82-8
• 化学式: C₆₂H₆₀O₁₄
• 分子量: 1029.15
• InChiKey: YHYKFQLXFFXEQT-QHQNJREQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  76
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  153
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  ethyl 3,4,6-tri-O-benzoyl-2-O-benzyl-1-thio-β-D-glucopyranoside 在 18-冠醚-6 、 三氟甲磺酸 、 溴 、 potassium carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 36.33h， 生成 methyl 2-O-benzyl-3,4,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  SFox 亚胺酯作为化学糖基化的多功能糖基供体

  摘要：

  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。

  DOI：

  10.1039/d4ob00679h

文献信息

• Co 2 (CO) 6 -propargyl cation mediates glycosylation reaction by using thioglycoside
  作者：Meng-jie Xia、Wang Yao、Xiang-bao Meng、Qing-hua Lou、Zhong-jun Li

  DOI：10.1016/j.tetlet.2017.05.012

  日期：2017.6

  glycosylation reaction by activating the thioglycoside donor. The glyco-oxacarbenium cation was formed by transferring the thio-aglycone to the cobalt-propargyl cation that was generated from the cobalt-propargylated acceptor in situ via the activating with Lewis acid. The reactivity of the donor (Armed or dis-armed) and the amount of the Lewis acid control the releasing rate of the cobalt-propargyl group.

  我们发现钴-炔丙基阳离子可以通过激活硫糖苷供体来介导糖基化反应。糖-氧杂碳鎓阳离子是通过将硫代糖苷配基转移到钴-炔丙基阳离子上而形成的，该钴-炔丙基阳离子是通过用路易斯酸活化就地从钴-炔丙基化的受体生成的。供体的反应性（武装或解除武装）和路易斯酸的量控制着钴炔丙基的释放速率。
• 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。
• 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。
• Thioperoxide-Mediated Activation of Thioglycoside Donors
  作者：Hongwen He、Xiangming Zhu

  DOI：10.1021/ol501211z

  日期：2014.6.6

  trimethylsilyl trifluoromethanesulfonate (TMSOTf) provides a powerful thiophilic promoter system, capable of activating different thioglycosides. Both armed and disarmed thioglycosides were activated effectively in the presence of different glycosyl acceptors, giving glycosidation products in high to excellent yields. A plausible activation pathway was also proposed and supported by isolating side-products

  硫过氧化物（1）与三甲基甲硅烷基三氟甲磺酸盐（TMSOTf）结合提供了强大的亲硫促进剂体系，能够活化不同的硫糖苷。在存在不同的糖基受体的情况下，武装和解除武装的硫代糖苷都被有效地激活，从而以高到极好的收率得到糖苷化产物。还提出了一条可行的活化途径，并通过分离副产物三氟甲基苯基二硫化物（CF 3 SSPh）和烯烃（42）予以支持。
• 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.