phenyl 2-azido-4-O-benzyl-(di-tert-butylsilylene)-2-deoxy-1-thio-α-D-glucopyranoside | 1447722-70-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-azido-4-O-benzyl-(di-tert-butylsilylene)-2-deoxy-1-thio-α-D-glucopyranoside
• 英文别名: (1R,6R,8R,9R,10R)-9-azido-3,3-ditert-butyl-10-phenylmethoxy-8-phenylsulfanyl-2,4,7-trioxa-3-silabicyclo[4.3.1]decane
• CAS: 1447722-70-4
• 化学式: C₂₇H₃₇N₃O₄SSi
• 分子量: 527.76
• InChiKey: UNDFRZUWWMBRAO-FXEFVXDJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.23
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  phenyl 2-azido-4-O-benzyl-(di-tert-butylsilylene)-2-deoxy-1-thio-α-D-glucopyranoside 在 二乙胺基三氟化硫 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 1.08h， 以52%的产率得到2-azido-4-O-benzyl-3,6-O-(di-tert-butylsilylene)-2-deoxy-1-fluoro-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
• 作为产物：
  描述：

  phenyl 3-O-acetyl-2-azido-4-O-benzyl-2-deoxy-1-thio-α-D-glucopyranoside 在 2,6-二甲基吡啶 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 phenyl 2-azido-4-O-benzyl-(di-tert-butylsilylene)-2-deoxy-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.