p-methylphenyl 2,3-di-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside | 220645-45-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-methylphenyl 2,3-di-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside
• 英文别名: [(2S,4aR,6S,7R,8S,8aS)-7-benzoyloxy-6-(4-methylphenyl)sulfanyl-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl] benzoate
• CAS: 220645-45-4
• 化学式: C₃₄H₃₀O₇S
• 分子量: 582.674
• InChiKey: IHYHWOMUUFMHGT-HZIHQJMLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  42
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  106
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  p-methylphenyl 2,3-di-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside 在 sodium tetrahydroborate 作用下， 以 乙腈 为溶剂， 反应 8.0h， 以75%的产率得到p-tolyl 2,3-di-O-benzoyl-4-O-benzyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  化学合成含有来自大肠杆菌 O74 的 O 抗原多糖四糖重复单元的稀有 D-Fuc3NAc

  摘要：

  来自大肠杆菌O74 的O抗原的四糖重复单元的化学合成是通过收敛的 [2 + 2] 嵌段合成策略来完成的。使用 DTBP 和 TIPST 介导的脱氧反应制备了具有挑战性的稀有 D-Fuc3NAc。其他单糖合成子是通过合理的保护基操作制备的，并且立体选择性糖基化是通过硫代糖苷或糖基三氯乙酰亚胺酯的活化来实现的。目标四糖以其 2-氨基乙基糖苷的形式制成，以促进进一步糖缀合物的形成，而不影响异头立体化学。

  DOI：

  10.1016/j.carres.2021.108366
• 作为产物：
  描述：

  苯甲醛二甲缩醛 在 吡啶 、 camphor-10-sulfonic acid 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 生成 p-methylphenyl 2,3-di-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Programmable One-Pot Oligosaccharide Synthesis

  摘要：

  In an effort to develop a broadly applicable approach to the facile one-pot synthesis of oligosaccharides, the reactivity of a number of p-methylphenyl thioglycoside (STol) donors which are either fully protected or have one hydroxyl group exposed has been quantitatively determined by HPLC. We have characterized and quantified the influence on reactivity of the structural effects of different monosaccharide cores and different protecting groups on each glycoside donor. In addition, we have established a correlation between glycosyl donor reactivity and the chemical shift of the anomeric proton by H-1 NMR. Using the reactivity data, we have created a database of thioglycosides as glycosyl donors and demonstrated its utility in the easy and rapid one-pot assembly of various linear and branched oligosaccharide structures. In addition, we have developed the first computer program, OptiMer, for use as a database search tool and guide for the selection of building blocks for the one-pot assembly of a desired oligosaccharide or a library of individual oligosaccharides.

  DOI：

  10.1021/ja982232s

文献信息

• Synthesis of the tetrasaccharide repeating unit of the O-antigen from Pseudomonas putida BIM B-1100 having rare D-Quip3NAc
  作者：Madhumita Bera、Balaram Mukhopadhyay

  DOI：10.1016/j.carres.2020.107955

  日期：2020.3

  Chemical synthesis of the complex tetrasaccharide repeating unit of the O-antigen from Pseudomonas putida BIM B-1100 is accomplished in the form of its 2-aminoethyl glycoside to leave the scope for further glycoconjugate formation without hampering the anomeric stereochemistry. A [2 + 2] strategy is followed to complete the total synthesis and a late stage TEMPO mediated oxidation is used to install

  来自恶臭假单胞菌BIM B-1100的O抗原的复杂四糖重复单元的化学合成以其2-氨基乙基糖苷的形式完成，从而为进一步的糖缀合物形成提供了范围，而不会妨碍异头异构体的立体化学。遵循[2 + 2]策略以完成总合成，并使用后期TEMPO介导的氧化来安装所需的糖醛酸。自由基介导的6-脱氧和随后的保护基操纵策略用于从合适的d-葡萄糖胺衍生物制备稀有的D-FucpNAc和D-Quip3NAc衍生物。
• Syntheses of Lewis^X and Dimeric Lewis^X:  Construction of Branched Oligosaccharides by a Combination of Preactivation and Reactivity Based Chemoselective One-Pot Glycosylations
  作者：Adeline Miermont、Youlin Zeng、Yuqing Jing、Xin-shan Ye、Xuefei Huang

  DOI：10.1021/jo701694k

  日期：2007.11.1

  dimeric LewisX, were assembled in one pot with high yields and exclusive regio- and stereoselectivities. p-Tolyl thioglycosides were utilized as the sole type of building blocks, thus simplifying the overall synthetic design. The reactivity-independent nature of the preactivation based method allows modular assembly of the dimeric LewisX octasaccharide without the need for tedious protective group manipulation

  两种不对称支链寡糖 Lewis X和二聚体 Lewis X以高产率和独特的区域和立体选择性在一锅中组装。对甲苯基硫糖苷被用作唯一类型的构建单元，从而简化了整体合成设计。基于预活化的方法的反应性独立性质允许二聚体路易斯X八糖的模块化组装，而无需繁琐的保护基操作来实现精确的异头反应。
• O,O-Dimethylthiophosphonosulfenyl bromide-silver triflate: a new powerful promoter system for the preactivation of thioglycosides
  作者：Peng Peng、Xin-Shan Ye

  DOI：10.1039/c0ob00380h

  日期：——

  O,O-Dimethylthiophosphonosulfenyl bromide (DMTPSB) in combination with silver triflate provides a powerful thiophilic promoter system. Both “armed” and “disarmed” thioglycoside glycosyl donors can be activated to form glycosidic linkages efficiently by the pre-activation protocol. The usefulness of this new promoter is illustrated by a successful iterative one-pot oligosaccharide assembly.

  O，O-二甲基硫代膦酰基磺酰基溴（DMTPSB）与三氟甲磺酸银提供了强大的亲硫性助催化剂系统。可以通过预激活方案将“武装的”和“解除武装的”硫代糖苷糖基供体两者活化，以有效地形成糖苷键。一个成功的迭代一锅寡糖组装说明了这种新启动子的有用性。
• A metal free mild and green approach for tandem opening of 4,6-O-benzylidene acetals to their corresponding 6-O-acetyl derivatives: Application in the synthesis of a trisaccharide using one-pot glycosylation reactions
  作者：Mana Mohan Mukherjee、Nabamita Basu、Shantanu Nandi、Rina Ghosh

  DOI：10.1016/j.carres.2019.03.002

  日期：2019.4

  An efficient and high yielding reaction for tandem opening of 4,6-O-benzylidene derivatives (gluco, galacto, manno, 2-phthalimido-2-deoxy glucosides) to their corresponding 6-O-acetyl derivatives has been established under metal free condition using 60% solution of aqueous acetic acid (v/v). The reaction is equally pertinent for large scale synthesis and also for disaccharide glycosides. Its application

  在无金属条件下，已经建立了一种高效，高产率的串联打开4,6-O-亚苄基衍生物（葡萄糖，半乳糖，甘露糖，2-邻苯二甲酰亚胺基-2-脱氧葡萄糖苷）为其相应的6-O-乙酰基衍生物的反应。使用60％的醋酸水溶液（v / v）。该反应对于大规模合成以及对二糖苷而言同样重要。还已经描述了其在构建用于利用一锅糖基化反应合成与铜绿假单胞菌有关的三糖部分的结构单元中的应用。
• Concise synthesis of the tetrasaccharide repeating unit of the O-antigen from Escherichia coli O131 containing N-acetyl neuraminic acid
  作者：Anirban Adak、Sakshi Balasaria、Balaram Mukhopadhyay

  DOI：10.1016/j.carres.2022.108654

  日期：2022.11

  Synthesis of the tetrasaccharide repeating unit of the O-antigen from E. coli O131 was accomplished through a linear strategy involving rationally protected monosaccharide units derived from commercially available sugars. The challenging α-glycosylation of N-acetyl neuraminic acid was achieved through activation of thioglycoside using NIS-mediated glycosylation strategy. The target tetrasaccharide

  来自大肠杆菌O131 的O抗原的四糖重复单元的合成是通过线性策略完成的，该策略涉及从市售糖衍生的合理保护的单糖单元。N-乙酰神经氨酸具有挑战性的 α-糖基化是通过使用 NIS 介导的糖基化策略激活硫糖苷来实现的。其 3-氨基丙基糖苷形式的目标四糖可用于进一步的糖缀合物形成而不妨碍异头立体化学。