phenyl 3,6-anhydro-2,4-di-O-benzyl-1-thio-α-D-glucopyranoside | 1447722-73-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 3,6-anhydro-2,4-di-O-benzyl-1-thio-α-D-glucopyranoside
• 英文别名: (1R,3R,4R,5S,8R)-4,8-bis(phenylmethoxy)-3-phenylsulfanyl-2,6-dioxabicyclo[3.2.1]octane
• CAS: 1447722-73-7
• 化学式: C₂₆H₂₆O₄S
• 分子量: 434.556
• InChiKey: QEBXFIBXIUYCML-WSGIOKLISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  62.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3,6-tri-O-acetyl-2,4-di-O-benzyl-α- and β-D-glucopyranose 在 吡啶 、 三氟化硼乙醚 、 sodium methylate 、 sodium hydride 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 99.0h， 生成 phenyl 3,6-anhydro-2,4-di-O-benzyl-1-thio-α-D-glucopyranoside
  参考文献：
  名称：

  Conformationally Armed 3,6-Tethered Glycosyl Donors: Synthesis, Conformation, Reactivity, and Selectivity

  摘要：

  The reactivity and selectivity of 3,6-tethered glycosyl donors have been studied using acceptors with different steric and electronic characteristics. Eight (four anomeric pairs) 3,6-bridged-glycosyl donors were synthesized in high yields from their common parent sugars. The glycosylation properties were tested using at least three different acceptors and several promoter systems. Thiophenyl 2,4-di-O-benzyl-3,6-O-(di-tert-butylsilylene)-alpha-D-glucopyranoside gave alpha/beta mixtures with standard NIS/TfOH mediated activation, whereas the corresponding fluoride was found to be highly beta-selective, when using SnCl2/AgE(C6F5)(4) as the promoter system. Mannosyl donors were highly alpha-selective despite the altered conformation. Galactosylations using NIS/TfOH were generally alpha-selective, but more beta-selective using the galactosyl fluoride and depending on the acceptor used. Thiophenyl 2-azido-2-deoxy-4-O-benzyl-3,6-O-(di-tert-butylsilylene)-alpha-D-glucopyranoside was found to be alpha-selective. The reactivity of the donors was investigated using competition experiments, and some but not all were found to be highly reactive. Generally it was found that the alpha-thioglycosides were significantly more reactive than the beta; this difference in reactivity was not found for 3,6-anhydro-, armed-(benzylated), or the classic super armed (silylated) donors. A mechanism supporting the unusual observations has been suggested.

  DOI：

  10.1021/jo4012464

文献信息

• Conformationally Armed 3,6-Tethered Glycosyl Donors: Synthesis, Conformation, Reactivity, and Selectivity
  作者：Mads Heuckendorff、Christian Marcus Pedersen、Mikael Bols

  DOI：10.1021/jo4012464

  日期：2013.7.19

  The reactivity and selectivity of 3,6-tethered glycosyl donors have been studied using acceptors with different steric and electronic characteristics. Eight (four anomeric pairs) 3,6-bridged-glycosyl donors were synthesized in high yields from their common parent sugars. The glycosylation properties were tested using at least three different acceptors and several promoter systems. Thiophenyl 2,4-di-O-benzyl-3,6-O-(di-tert-butylsilylene)-alpha-D-glucopyranoside gave alpha/beta mixtures with standard NIS/TfOH mediated activation, whereas the corresponding fluoride was found to be highly beta-selective, when using SnCl2/AgE(C6F5)(4) as the promoter system. Mannosyl donors were highly alpha-selective despite the altered conformation. Galactosylations using NIS/TfOH were generally alpha-selective, but more beta-selective using the galactosyl fluoride and depending on the acceptor used. Thiophenyl 2-azido-2-deoxy-4-O-benzyl-3,6-O-(di-tert-butylsilylene)-alpha-D-glucopyranoside was found to be alpha-selective. The reactivity of the donors was investigated using competition experiments, and some but not all were found to be highly reactive. Generally it was found that the alpha-thioglycosides were significantly more reactive than the beta; this difference in reactivity was not found for 3,6-anhydro-, armed-(benzylated), or the classic super armed (silylated) donors. A mechanism supporting the unusual observations has been suggested.