trichloroacetimido 2-azido-3-O-(tert-butyldimethylsilyl)-4,6-O-isopropylidene-β-D-glucopyranoside | 147158-36-9

• 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: trichloroacetimido 2-azido-3-O-(tert-butyldimethylsilyl)-4,6-O-isopropylidene-β-D-glucopyranoside
• 英文别名: [(4aR,6S,7R,8R,8aR)-7-azido-8-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl] 2,2,2-trichloroethanimidate
• CAS: 147158-36-9
• 化学式: C₁₇H₂₉Cl₃N₄O₅Si
• 分子量: 503.886
• InChiKey: NGEJGBJTJXDBQE-VEGXAWMVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.94
• 拓扑面积：
  84.4
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  trichloroacetimido 2-azido-3-O-(tert-butyldimethylsilyl)-4,6-O-isopropylidene-β-D-glucopyranoside 在 钯 吡啶 、 potassium fluoride 、 甲酸 、 bis(triphenylphosphine)palladium(II)-chloride 、 二甲基硫 、 三乙基硼 、 三氟甲磺酸 、 4 A molecular sieve 、 三正丁基氢锡 、 苯硒酚 、 potassium carbonate 、 一水合肼 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 45.51h， 生成 tert-butyl 3-[(2R,3R,4S,5R)-5-[(1R)-2-[(2R,3R,4R,5R,6S)-6-[[(4aR,6R,7R,8R,8aR)-7-acetamido-8-[tert-butyl(dimethyl)silyl]oxy-2,2-dimethyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-6-yl]oxy]-5-amino-3,4-dihydroxyoxan-2-yl]-1-hydroxyethyl]-3,4-dihydroxyoxolan-2-yl]-2,6-dioxopyrimidine-1-carboxylate
  参考文献：
  名称：

  Synthetic Studies of the Tunicamycin Antibiotics. Preparation of (+)-Tunicaminyluracil, (+)-Tunicamycin-V, and 5'-epi-Tunicamycin-V

  摘要：

  A concise synthetic route to the tunicamycin antibiotics is described, illustrated by the preparation of (+)-tunicamycin-V (1-V). Key features of the synthesis include (1) the development and application of a silicon-mediated reductive coupling of aldehydes and allylic alcohols to construct the undecose core of the natural product and (2) the development of an efficient procedure for the synthesis of the trehalose glycosidic bond within the antibiotic. These innovations allow for the coupling of a uridine-derived aldehyde fragment with a performed trehalose-linked disaccharide allylic alcohol to form the carbohydrate core (1) of the natural product in a highly covergent manner. The resultant amino polyol is a versatile intermediate for the synthesis of any of the homologous tunicamycin antibiotics.

  DOI：

  10.1021/ja00090a018
• 作为产物：
  描述：

  三氯乙腈 、 (4aR,7R,8R,8aR)-7-azido-8-((tert-butyldimethylsilyl)oxy)-2,2-dimethylhexahydropyrano[3,2-d][1,3]dioxin-6-ol 在 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以64%的产率得到trichloroacetimido 2-azido-3-O-(tert-butyldimethylsilyl)-4,6-O-isopropylidene-β-D-glucopyranoside
  参考文献：
  名称：

  Synthetic Studies of the Tunicamycin Antibiotics. Preparation of (+)-Tunicaminyluracil, (+)-Tunicamycin-V, and 5'-epi-Tunicamycin-V

  摘要：

  A concise synthetic route to the tunicamycin antibiotics is described, illustrated by the preparation of (+)-tunicamycin-V (1-V). Key features of the synthesis include (1) the development and application of a silicon-mediated reductive coupling of aldehydes and allylic alcohols to construct the undecose core of the natural product and (2) the development of an efficient procedure for the synthesis of the trehalose glycosidic bond within the antibiotic. These innovations allow for the coupling of a uridine-derived aldehyde fragment with a performed trehalose-linked disaccharide allylic alcohol to form the carbohydrate core (1) of the natural product in a highly covergent manner. The resultant amino polyol is a versatile intermediate for the synthesis of any of the homologous tunicamycin antibiotics.

  DOI：

  10.1021/ja00090a018

文献信息

• A convergent synthetic route to the tunicamycin antibiotics. Synthesis of (+)-tunicamycin V
  作者：Andrew G. Myers、David Y. Gin、Daniel H. Rogers

  DOI：10.1021/ja00058a060

  日期：1993.3

  synthetic route to the tunicamycin antibiotics is described, illustrated by the preparation of (+)-tunicamycin-V (1-V). Key features of the synthesis include: (1) the development and application of a silicon-mediated reductive coupling of aldehydes and allylic alcohols to construct the undecose core of the natural product; and (2) the development of an efficient procedure for the synthesis of the trehalose

  描述了衣霉素抗生素的简明合成路线，以 (+)-衣霉素-V (1-V) 的制备为例进行了说明。该合成的主要特点包括：（1）硅介导的醛和烯丙醇还原偶联的开发和应用，以构建天然产物的未脱糖核；(2) 开发一种有效的方法来合成抗生素内的海藻糖糖苷键。这些创新允许尿苷衍生的醛片段与预先形成的海藻糖连接的二糖烯丙醇偶联，以高度收敛的方式形成天然产物的碳水化合物核心 (1)。所得氨基多元醇是用于合成任何同源衣霉素抗生素的通用中间体。