p-tolyl 4,6-di-O-benzylidenyl-3-O-benzyl-1-thio-2-azido-2-deoxy-D-galactopyranoside | 1310050-38-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: p-tolyl 4,6-di-O-benzylidenyl-3-O-benzyl-1-thio-2-azido-2-deoxy-D-galactopyranoside
• 英文别名: p-tolyl 2-azido-4,6-O-benzylidene-3-O-benzyl-2-deoxy-thio-α-D-galactopyranoside；(2S,4aR,7R,8R,8aR)-7-azido-6-(4-methylphenyl)sulfanyl-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 1310050-38-4
• 化学式: C₂₇H₂₇N₃O₄S
• 分子量: 489.595
• InChiKey: LSFXJSWSDKKNNC-BMWMBDNNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  76.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  p-tolyl 4,6-di-O-benzylidenyl-3-O-benzyl-1-thio-2-azido-2-deoxy-D-galactopyranoside 在 camphor-10-sulfonic acid 作用下， 以 甲醇 为溶剂， 反应 2.0h， 以90%的产率得到(2R,3R,4R,5R)-5-azido-2-(hydroxymethyl)-6-(4-methylphenyl)sulfanyl-4-phenylmethoxyoxan-3-ol
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157
• 作为产物：
  描述：

  4-methylphenyl 2-azido-4,6-O-benzylidene-2-deoxy-1-thio-β-D-galactopyranoside 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 4.5h， 生成 p-tolyl 4,6-di-O-benzylidenyl-3-O-benzyl-1-thio-2-azido-2-deoxy-D-galactopyranoside
  参考文献：
  名称：

  碳水化合物底物的亚化学计量还原醚化和一锅保护基操纵。

  摘要：

  在这项研究中，我们报告了一种新的还原性醚化程序，用于保护碳水化合物底物及其在单罐糖基结构单元制备中的应用。所报道的方法的特征在于使用聚甲基氢硅氧烷（PMHS）作为亚化学计量的还原剂，可防止反硅烷化副反应并提高还原醚化方法的效率。描述了PMHS还原醚化方法在一锅保护基操纵中的应用。

  DOI：

  10.1039/d0ob00252f

文献信息

• Application of 2-Azido-2-deoxythioglycosides for β-Glycoside Formation and Oligosaccharide Synthesis
  作者：Kwok-Kong Tony Mong、Yu-Fang Yen、Wei-Cheng Hung、Yen-Hsun Lai、Jiun-Han Chen

  DOI：10.1002/ejoc.201200173

  日期：2012.5

  configuration. This study investigated the use of 2-azido-2-deoxythioglycosides for 1,2-trans-β-glycosidic bond formation under low-concentration glycosylation conditions. Further application of the 2-azido-2-deoxythioglycosyl substrates for one-pot oligosaccharide synthesis was demonstrated in the synthesis of protected β-(16)-N-acetylglucosamine trimer, core-6–serine conjugate, and F1–α serine conjugate.

  大多数天然 2-乙酰氨基-2-脱氧糖苷以 1,2-反式-β-糖苷构型存在。本研究调查了 2-叠氮基-2-脱氧硫糖苷在低浓度糖基化条件下用于 1,2-反式-β-糖苷键形成的用途。2-叠氮基-2-脱氧硫糖基底物在一锅寡糖合成中的进一步应用在受保护的β-(16)-N-乙酰氨基葡萄糖三聚体、核心6-丝氨酸偶联物和F1-α丝氨酸偶联物的合成中得到了证明。
• Dimethylformamide: An Unusual Glycosylation Modulator
  作者：Shao-Ru Lu、Yen-Hsun Lai、Jiun-Han Chen、Chih-Yueh Liu、Kwok-Kong Tony Mong

  DOI：10.1002/anie.201100076

  日期：2011.8.1

  A simple solution: When N,N‐dimethylformamide was used to direct the stereochemical course of glycosylation reactions, 1,2‐cis glycosylation products were formed with excellent selectivity. A straightforward highly α‐stereoselective glycosylation involving preactivation (see scheme) should find broad application and be especially useful for sequential glycosylation reactions to form oligosaccharides

  一个简单的解决方案：当使用N，N-二甲基甲酰胺指导糖基化反应的立体化学过程时，会形成1,2-顺式糖基化产物，选择性极好。涉及预激活的直接的高度α-立体选择性糖基化反应（请参见方案）应该得到广泛的应用，对于顺序糖基化反应形成寡糖特别有用。LG =离开小组。
• 4,6-Di-O-Benzylidenyl group-directed preparation of 2-deoxy-2-azido-α-d-galactopyranosides promoted by 3-O-TBDPS
  作者：Xing-Yong Liang、Jing Yang、Zhong-Hao Qiu、Lei Wang、Todd L. Lowary、Hua-Jun Shawn Fan

  DOI：10.1016/j.carres.2021.108237

  日期：2021.2

  In this study, we designed a method to prepare 2-deoxy-2-azido-α-d-galactopyranosidic bonds using 4,6-di-O-benzylidenyl-3-O-t-butyldiphenylsilyl protected 2-deoxy-2-azido-1-thio-d-galactopyranoside 5 as donors. The donor 5 gives a good to excellent α-selectivity in the glycosylation with secondary alcohols, which was found to be associated with the benzylidenyl on 4,6-di-O and TBDPS on 3-O of the donor

  在这项研究中，我们设计了一种使用4,6-二-O-苄叉基-3-叔丁基二苯基甲硅烷基保护的2-脱氧-2-叠氮基-1制备2-脱氧-2-叠氮基-α-d-吡喃半乳糖苷键的方法。 -硫代-d-吡喃半乳糖苷5作为供体。供体5在与仲醇的糖基化中具有良好的优异的α-选择性，这与供体5的4，6-二-O上的亚苄基和3-O上的TBDPS有关。供体6和7，3-O-TBDPS可以增加硫糖苷的活性，而4,6-二-O-苄基上的孤对增强了gg-协同作用，这在提高立体选择性方面发挥了作用。最后，通过合成含α-半乳糖胺的五糖26证明了该方法。