2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranosyl O-methyl phenylcarbamothioate | 1258410-92-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranosyl O-methyl phenylcarbamothioate
• 英文别名: SNea carbamothioate；[(2R,3R,4S,5R,6S)-3,4,5-tribenzoyloxy-6-(C-methoxy-N-phenylcarbonimidoyl)sulfanyloxan-2-yl]methyl benzoate
• CAS: 1258410-92-2
• 化学式: C₄₂H₃₅NO₁₀S
• 分子量: 745.807
• InChiKey: DACLZAJVRVWVHX-WIESDFACSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  54
• 可旋转键数：
  17
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  161
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  甲基2,3,6-三-O-苄基-ALPHA-D-吡喃葡萄糖苷 、 2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranosyl O-methyl phenylcarbamothioate 在 copper(II) bis(trifluoromethanesulfonate) 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 1.5h， 以78%的产率得到methyl 4-O-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Glycosyl Alkoxythioimidates as Complementary Building Blocks for Chemical Glycosylation

  摘要：

  It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation experiments in the presence of various promoters. The results obtained indicate that SNea carbamothioates have a very similar reactivity profile to that of glycosyl thiocyanates, yet are significantly more stable and tolerate selected protecting group manipulations. These features make the SNea carbamothioates new promising building blocks for further utilization in

  DOI：

  10.1021/ol1023079
• 作为产物：
  描述：

  methyl N-phenylthiocarbamate 在 吡啶 、 sodium methylate 、 sodium hydroxide 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 2.0h， 生成 2,3,4,6-tetra-O-benzoyl-1-thio-β-D-glucopyranosyl O-methyl phenylcarbamothioate
  参考文献：
  名称：

  Glycosyl Alkoxythioimidates as Complementary Building Blocks for Chemical Glycosylation

  摘要：

  It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation experiments in the presence of various promoters. The results obtained indicate that SNea carbamothioates have a very similar reactivity profile to that of glycosyl thiocyanates, yet are significantly more stable and tolerate selected protecting group manipulations. These features make the SNea carbamothioates new promising building blocks for further utilization in

  DOI：

  10.1021/ol1023079

文献信息

• Glycosyl alkoxythioimidates as building blocks for glycosylation: a reactivity study
  作者：Sneha C. Ranade、Alexei V. Demchenko

  DOI：10.1016/j.carres.2014.06.025

  日期：2015.2

  Structural modifications of the leaving group of S-glycosyl O-methyl phenylcarbamothioates (SNea) involving change of substituents that express different electronic effects led to a better understanding of how the reactivity of these glycosyl donors can be modified by changing the structure of their leaving groups. Mechanistic studies involving the isolation of departed aglycones were indicative of

  S-糖基O-甲基苯基氨基甲磺酸酯（SNea）的离去基团的结构修饰涉及到表现出不同电子效应的取代基的变化，从而使人们对如何通过改变其离去基团的结构来修饰这些糖基供体的反应性有了更好的理解。 。涉及离去的糖苷配基分离的机理研究表明，通过异头硫而不是远端氮原子直接激活对甲氧基-SNea和对硝基-SNea离开基团。给电子取代基（对甲氧基）的存在对硫原子的亲核性具有强烈的影响，该硫原子的亲核性尤其容易受到亲硫试剂的攻击。该关键观察结果使得能够区分对甲氧基-SNea与对硝基-SNea以及甚至未修饰的SNea离去基团的反应性水平。在一系列SNea离去基团中观察到的反应性差异足以通过选择性激活策略用于快速寡糖合成。
• A Comparative Study of Glycosyl Thioimidates as Building Blocks for Chemical Glycosylation
  作者：Sneha C. Ranade、Scott J. Hasty、Alexei V. Demchenko

  DOI：10.1080/07328303.2013.826670

  日期：2013.7.24

  Our results indicate that the reactivity and the activation profile of thioimidate glycosyl donors vary significantly depending on the endocyclic heteroatom (N,O,S). Reactivity diminishes in accordance with the following sequence: O > S > N; and this trend stands for a majority of promoters tested. Acyclic glycosyl thioimidates were found to be generally less reactive than the respective cyclic counterparts. The difference in the reactivity was confirmed in direct competition experiments. These findings made possible a two-step one-pot selective activation using thioimidates as the anomeric leaving group of the glycosyl donor and temporary masking group of the glycosyl acceptor. Supplemental materials are available for this article. Go to the publisher's online edition of Journal of Carbohydrate Chemistry to view the supplemental file.
• Glycosyl Alkoxythioimidates as Complementary Building Blocks for Chemical Glycosylation
  作者：Sneha C. Ranade、Sophon Kaeothip、Alexei V. Demchenko

  DOI：10.1021/ol1023079

  日期：2010.12.17

  It is reported that S-glycosyl O-methyl phenylcarbamothioates (SNea carbamothioates) have a fully orthogonal character in comparison to S-benzoxazolyl (SBox) glycosides. This complete orthogonality was revealed by performing competitive glycosylation experiments in the presence of various promoters. The results obtained indicate that SNea carbamothioates have a very similar reactivity profile to that of glycosyl thiocyanates, yet are significantly more stable and tolerate selected protecting group manipulations. These features make the SNea carbamothioates new promising building blocks for further utilization in