(3-endo,6-endo)-6-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-(hydroxymethyl)-3-methyl-7-oxabicyclo<2.2.1>heptan-2-one | 142041-39-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: (3-endo,6-endo)-6-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-(hydroxymethyl)-3-methyl-7-oxabicyclo<2.2.1>heptan-2-one
• 英文别名: (1S,3S,4R,6R)-6-[tert-butyl(dimethyl)silyl]oxy-1-(hydroxymethyl)-3-methyl-7-oxabicyclo[2.2.1]heptan-2-one
• CAS: 142041-39-2
• 化学式: C₁₄H₂₆O₄Si
• 分子量: 286.444
• InChiKey: GMDNMPHDQFXAOJ-OXIWPEFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3-endo,6-endo)-6-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-(hydroxymethyl)-3-methyl-7-oxabicyclo<2.2.1>heptan-2-one 在 四丙基高钌酸铵 、 3 A molecular sieve 、 N-甲基吗啉氧化物 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (3-endo,6-endo)-6-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-3-methyl-2-oxo-7-oxabicyclo<2.2.1>heptane-2-carboxaldehyde
  参考文献：
  名称：

  Synthetic studies on furanoheliangolides. Stereocontrolled construction of the oxygen-bridged tricyclic framework

  摘要：

  The heavily functionalized 6,9-epoxycyclodeca[b]furan-11-ones 34 and 37 have been prepared in 13 steps from 4-methyl-2-[(phenylmethoxy)methyl]furan. The key elements of the scheme include a high-pressure Diels-Alder cycloaddition to 1-cyanovinyl acetate, highly regioselective hydroboration, controlled stepwise oxidation to give keto aldehyde 20, and thermal oxy-Cope rearrangement of both 32 and 36b. The prior introduction of a phenylthio substituent provides for the accommodation of different levels of unsaturation at a more advanced stage of furanoheliangolide construction. While the present strategy is developed around a racemic model, the potential for adoption of enantioselective features is immediate. The overall stereocontrolled sequence provides a general and flexible entry into oxygen-bridged frameworks closely related to substructures occurring in many furan-type germacranolides.

  DOI：

  10.1021/jo00042a036
• 作为产物：
  描述：

  methyl 4-methyl-2-<(phenylmethoxy)methyl>-3-furancarboxylate 在 palladium on activated charcoal 咪唑 、 喹啉 、 氢氧化钾 、 lithium hydroxide 、 sodium hydroxide 、 聚合甲醛 、 四丙基高钌酸铵 、 硼烷四氢呋喃络合物 、 3 A molecular sieve 、 氢气 、 双氧水 、 铜 、 二异丁基氢化铝 、 N-甲基吗啉氧化物 、 对苯二酚 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -78.0~25.0 ℃ 、1206.58 MPa 条件下， 反应 432.08h， 生成 (3-endo,6-endo)-6-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-1-(hydroxymethyl)-3-methyl-7-oxabicyclo<2.2.1>heptan-2-one
  参考文献：
  名称：

  Synthetic studies on furanoheliangolides. Stereocontrolled construction of the oxygen-bridged tricyclic framework

  摘要：

  The heavily functionalized 6,9-epoxycyclodeca[b]furan-11-ones 34 and 37 have been prepared in 13 steps from 4-methyl-2-[(phenylmethoxy)methyl]furan. The key elements of the scheme include a high-pressure Diels-Alder cycloaddition to 1-cyanovinyl acetate, highly regioselective hydroboration, controlled stepwise oxidation to give keto aldehyde 20, and thermal oxy-Cope rearrangement of both 32 and 36b. The prior introduction of a phenylthio substituent provides for the accommodation of different levels of unsaturation at a more advanced stage of furanoheliangolide construction. While the present strategy is developed around a racemic model, the potential for adoption of enantioselective features is immediate. The overall stereocontrolled sequence provides a general and flexible entry into oxygen-bridged frameworks closely related to substructures occurring in many furan-type germacranolides.

  DOI：

  10.1021/jo00042a036

文献信息

• Synthetic studies on furanoheliangolides. Stereocontrolled construction of the oxygen-bridged tricyclic framework
  作者：Dearg S. Brown、Leo A. Paquette

  DOI：10.1021/jo00042a036

  日期：1992.7

  The heavily functionalized 6,9-epoxycyclodeca[b]furan-11-ones 34 and 37 have been prepared in 13 steps from 4-methyl-2-[(phenylmethoxy)methyl]furan. The key elements of the scheme include a high-pressure Diels-Alder cycloaddition to 1-cyanovinyl acetate, highly regioselective hydroboration, controlled stepwise oxidation to give keto aldehyde 20, and thermal oxy-Cope rearrangement of both 32 and 36b. The prior introduction of a phenylthio substituent provides for the accommodation of different levels of unsaturation at a more advanced stage of furanoheliangolide construction. While the present strategy is developed around a racemic model, the potential for adoption of enantioselective features is immediate. The overall stereocontrolled sequence provides a general and flexible entry into oxygen-bridged frameworks closely related to substructures occurring in many furan-type germacranolides.