4,6-Di-O-isopropylidene-3-O-(2-bromo-1-ethoxyethyl)-D-glucal

• 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: 4,6-Di-O-isopropylidene-3-O-(2-bromo-1-ethoxyethyl)-D-glucal
• 英文别名: (4aR,8R,8aS)-8-(2-bromo-1-ethoxyethoxy)-2,2-dimethyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxine
• 化学式: C₁₃H₂₁BrO₅
• 分子量: 337.211
• InChiKey: OFIUVRSEOXLLJJ-QFEGIVONSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,6-Di-O-isopropylidene-3-O-(2-bromo-1-ethoxyethyl)-D-glucal 在 偶氮二异丁腈 吡啶 、 三正丁基氢锡 、 溶剂黄146 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 Acetic acid (2R,3aR,4S,6R,7S,7aR)-6-acetoxymethyl-4-cyano-2-ethoxy-hexahydro-furo[3,2-c]pyran-7-yl ester
  参考文献：
  名称：

  Serial radical reactions of enol ethers: ready routes to highly functionalized C-glycosyl derivatives

  摘要：

  DOI：

  10.1021/ja00191a064
• 作为产物：
  描述：

  4,6-O-异亚丙基-D-葡萄糖醛 、 1,2-二溴乙氧基乙烷 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 4,6-Di-O-isopropylidene-3-O-(2-bromo-1-ethoxyethyl)-D-glucal
  参考文献：
  名称：

  Serial Radical Reactions of Glycals: Ready Routes to Highly Functionalized C-Glycosyl Derivatives

  摘要：

  The C3-OH of partially protected glycals can be readily converted into mixed acetals of 2-bromoacetaldehyde or into silylmethylene bromides. Reaction of these derivatives with tri-n-butyltin hydride gives a radical that cyclizes efficiently to generate a stabilized radical at C1. The latter can be trapped very efficiently with acrylonitrile, tert-butyl isocyanide, allyltri-n-butyltin, tributyltin acrylates, or a complex pyranoside enone to afford C-glycosides in which a 1,2 disubstitution has taken place. The stereochemistry of the resulting 1,2 disubstituted product is dependent, at C-2, on the stereochemistry of the C3-OH and at the anomeric center (C-1) upon the interplay of (a) steric effects and (b) the electronic bias of the radical anomeric effect.

  DOI：

  10.1021/jo00117a044

文献信息

• Serial Radical Reactions of Glycals: Ready Routes to Highly Functionalized C-Glycosyl Derivatives
  作者：J. Cristobal Lopez、Ana M. Gomez、Bert Fraser-Reid

  DOI：10.1021/jo00117a044

  日期：1995.6

  The C3-OH of partially protected glycals can be readily converted into mixed acetals of 2-bromoacetaldehyde or into silylmethylene bromides. Reaction of these derivatives with tri-n-butyltin hydride gives a radical that cyclizes efficiently to generate a stabilized radical at C1. The latter can be trapped very efficiently with acrylonitrile, tert-butyl isocyanide, allyltri-n-butyltin, tributyltin acrylates, or a complex pyranoside enone to afford C-glycosides in which a 1,2 disubstitution has taken place. The stereochemistry of the resulting 1,2 disubstituted product is dependent, at C-2, on the stereochemistry of the C3-OH and at the anomeric center (C-1) upon the interplay of (a) steric effects and (b) the electronic bias of the radical anomeric effect.
• Serial radical reactions of enol ethers: ready routes to highly functionalized C-glycosyl derivatives
  作者：J. Cristobal Lopez、Bert Fraser-Reid

  DOI：10.1021/ja00191a064

  日期：1989.4