6-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose | 173395-55-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
• 英文别名: 1,2:3,4-di-O-isopropylidene-6-O-(2,3,4,6-tetra-O-benzyl-α,β-D-glucopyranosyl)-α-D-galactopyranose；(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-8-[[(3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxymethyl]-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecane
• CAS: 173395-55-6
• 化学式: C₄₆H₅₄O₁₁
• 分子量: 782.928
• InChiKey: XIBZGKIHGHEEHR-SIXZBANTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  57
• 可旋转键数：
  16
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为产物：
  描述：

  2-Nitrobenzyl-2,3,4,6-tetra-O-acetyl-β-D-glucopyranosid 在 甲醇 、 三(五氟苯基)硼烷 、 sodium methylate 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.58h， 生成 6-O-(2,3,4,6-tetra-O-benzyl-D-glucopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  Tiwari, Varsha; Badavath, Vishnu Nayak; Singh, Adesh Kumar, Journal of the Indian Chemical Society, 2020, vol. 97, # 2, p. 227 - 236

  摘要：

  DOI：

文献信息

• An efficient glycosylation protocol with glycosyl ortho-alkynylbenzoates as donors under the catalysis of Ph3PAuOTf
  作者：Yao Li、You Yang、Biao Yu

  DOI：10.1016/j.tetlet.2008.04.017

  日期：2008.5

  A new and powerful glycosylation protocol with glycosyl ortho-alkynylbenzoates as donors and Ph3PAuOTf as a promoter is disclosed. The donors are readily available and stable; the glycosidic coupling yields are generally excellent; the promotion system is catalytic, neutral, and orthogonal to the known glycosylation conditions.

  公开了一种新的且功能强大的糖基化方案，其中糖基邻炔基苯甲酸酯为供体，Ph 3 PAuOTf为启动子。捐助者随时可用且稳定；糖苷偶联的产量通常是优异的；促进系统是催化的，中性的，并且与已知的糖基化条件正交。
• Reconsidering glycosylations at high temperature: precise microwave heating
  作者：Kim Larsen、Kasper Worm-Leonhard、Peter Olsen、Andreas Hoel、Knud J. Jensen

  DOI：10.1039/b511266d

  日期：——

  Current methods for glycosylation of complex alcohols, e.g. with glycosyl trichloroacetimidates, generally occur in the presence of a strong Lewis acid ‘promoter’, and at sub-ambient temperatures. However, the older literature reports high-temperature glycosylations, especially of phenols. We have described an efficient method for glycosylation of alcohols under neutral conditions, using as anomeric leaving group methyl 3,5-dinitrosalicylate (DISAL). Only a very few reports have described the use of microwaves to promote glycosylations, mainly of simple alcohols. Here we describe fast, high-temperature glycosylations using precise microwave heating in the synthesis of oligosaccharides, with both DISAL and widely used trichloroacetimidate glycosyl donors in the absence of strong Lewis acids. Also, we have applied microwave heating as a general protocol for evaluating new, potential glycosyl donors.

  目前用于复杂醇类（如使用糖基三氯乙酰亚胺酸酯）的糖基化方法通常在强Lewis酸“促进剂”存在下，并在亚环境温度下进行。然而，早期的文献报道了高温下的糖基化反应，特别是酚类的糖基化。我们已经描述了一种在中性条件下使用异头离去基团甲基3,5-二硝基水杨酸酯（DISAL）进行醇类糖基化的高效方法。仅有极少数报道描述了使用微波促进糖基化反应，主要是简单醇类。在这里，我们描述了在不含强Lewis酸的情况下，使用精确微波加热在寡糖合成中进行快速、高温糖基化反应，同时使用DISAL和广泛应用的三氯乙酰亚胺酸酯糖基供体。此外，我们还将微波加热作为一种通用协议，用于评估新的潜在糖基供体。
• Synthesis of Anomeric Sulfimides and Their Use as a New Family of Glycosyl Donors
  作者：Florence Chéry、Stéphanie Cassel、Hans Peter Wessel、Patrick Rollin

  DOI：10.1002/1099-0690(20021)2002:1<171::aid-ejoc171>3.0.co;2-7

  日期：2002.1

  We introduce a convenient synthesis of anomeric sulfimides, the ability of which to act as glycosyl donors has been tested with various thiophilic reagents and acceptors.

  我们介绍了一种方便的异头磺酰亚胺合成方法，其作为糖基供体的能力已经用各种亲硫试剂和受体进行了测试。
• Glycosyl<i>ortho</i>-Methoxybenzoates: Catalytically Activated Glycosyl Donors with an Easily Removable and Recyclable Leaving Group
  作者：Steffan K. Kristensen、Stéphane Salamone、Michelle R. Rasmussen、Mikkel H. S. Marqvorsen、Henrik H. Jensen

  DOI：10.1002/ejoc.201600747

  日期：2016.11

  p-cyano-o-methoxybenzoate donors. In glycosylation reactions with o-methoxybenzoate donors, the yields of disaccharide products were good to excellent for various glycosyl acceptors, including a carbohydrate-based secondary alcohol. Furthermore, β-selective mannosylation was achieved with a Crich-type donor at 0 °C to ambient temperature, without donor preactivation. The donor was also used for the first

  我们将 β-邻甲氧基苯甲酸酯描述为一种用于催化化学糖基化的储存稳定且实用的 C-1 核离心剂，其中苯甲酸副产物可以很容易地去除、重新分离，并可能在糖基化反应后回收。这种新型糖基供体可以通过一系列促进剂有效活化，包括 Bi(OTf)3、Fe(OTf)3、TMSOTf（TMS = 三甲基甲硅烷基）和三氟甲磺酸，催化剂用量低（<10 mol-%）负荷。供体显示出比类似的苯甲酸盐、对甲氧基苯甲酸盐和对氰基-邻甲氧基苯甲酸盐供体更高的反应性。在与邻甲氧基苯甲酸酯供体的糖基化反应中，对于各种糖基受体（包括基于碳水化合物的仲醇），二糖产物的产率从好到极好。此外，β-选择性甘露糖基化是用 Crich 型供体在 0°C 至环境温度下实现的，无需供体预活化。供体也用于一锅两步糖基化的第一步，得到三糖；第二个偶联涉及用 NIS/TMSOTf（NIS = N-碘代琥珀酰亚胺）激活硫糖苷。我们相信这为当前协议提供了一个很好的替代方案。
• A Streamlined Regenerative Glycosylation Reaction: Direct, Acid‐Free Activation of Thioglycosides
  作者：Samira Escopy、Yashapal Singh、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1002/chem.202003479

  日期：2021.1.4

  (HOFox) is able to mediate glycosylations via intermediacy of OFox imidates. Thioglycoside precursors were first converted into the corresponding glycosyl bromides that were then converted into the OFox imidates in the presence of Ag2O followed by the activation with catalytic Lewis acid in a regenerative fashion. Reported herein is a direct conversion of thioglycosides via the regenerative approach

  我们的小组之前曾报道过，3,3-二氟吲哚（HOFox）能够通过 OFox 亚胺酸酯的中介来介导糖基化。硫糖苷前体首先转化为相应的糖基溴化物，然后在 Ag 2 O存在下转化为 OFox 亚胺酸酯，然后以再生方式用催化路易斯酸活化。本文报道了通过再生方法直接转化硫糖苷，该方法绕过了溴化物的中介并消除了对基于重金属的促进剂的需要。在中性反应条件下仅使用 1 当量即可实现硫糖苷的直接再生活化。不含酸性添加剂的 NIS 和催化 HOFox。