4-(7-benzo[b]thien-2-yl-1-hydroxyheptyl)-2-trimethylsilylfuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噻吩类
• 英文名称: 4-(7-benzo[b]thien-2-yl-1-hydroxyheptyl)-2-trimethylsilylfuran
• 英文别名: 7-(1-benzothiophen-2-yl)-1-(5-trimethylsilylfuran-3-yl)heptan-1-ol
• 化学式: C₂₂H₃₀O₂SSi
• 分子量: 386.63
• InChiKey: QCYXGPYCIYTJRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.27
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  61.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(7-benzo[b]thien-2-yl-1-hydroxyheptyl)-2-trimethylsilylfuran 在 吡啶 、 乙酸酐 作用下， 生成 4-(1-acetoxy-7-benzo[b]thien-2-ylheptyl)-2-trimethylsilylfuran
  参考文献：
  名称：

  Anti-inflammatory furanones

  摘要：

  新的具有抗炎、免疫抑制和抗增殖活性的5-羟基-2-呋喃酮化合物对治疗牛皮癣和调节钙稳态具有用处。

  公开号：

  US05134128A1
• 作为产物：
  描述：

  2-(trimethylsilyl)-4-furaldehyde 、 6-(benzo[b]thien-2-yl)-1-bromohexane 在 magnesium 作用下， 生成 4-(7-benzo[b]thien-2-yl-1-hydroxyheptyl)-2-trimethylsilylfuran
  参考文献：
  名称：

  Singlet oxygen oxidation of substituted furans to 5-hydroxy-2(5H)-furanone

  摘要：

  The conditions for the regiospecific singlet oxygen oxidation of various 2,4-disubstituted furans 9 to 4-substituted-2 (5H)-furanones 3 are developed. The presence of a C-2 substituent (e.g., trimethylsilyl, tert-butyldimethylsilyl, or tributylstannyl) in 9 is an absolute requirement for the formation of the 4-substituted-5-hydroxy-2(5H)-furanone regioisomer 3. When the C-2 substituent is triethylsilyl (TES) or TBDMS, however, apart from 3, the corresponding 5-trialkylsiloxy derivative 11 is also isolated in a significant amount. These silyl acetals are unexpectedly stable but can be hydrolyzed back to 3 on stirring with dilute acid. The formation of silyl acetals, to our knowledge, has never been reported in the singlet oxygen oxidation of (trialkylsilyl)furan. A plausible mechanism for their formation is proposed. The presence of a catalytic amount of water in the oxidation of 2-(trialkylsilyl)-4-substituted-furans not only eliminates the formation of the silyl acetals but also speeds up the rate of the oxidation process. Moreover, the oxidation can then be carried out at 0-degrees-C instead of at -78-degrees-C. Oxidation of 2-(1-hydroxyalkyl)-4-substituted-furans in the absence of a reducing agent gives little or no sign of 2,5-disubstituted-6-hydroxy-3(2H)-pyranone 23 but instead 26 selectively. Thus, the (1-hydroxy)alkyl group can be utilized as the trialkylsilyl or trialkylstannyl group in dictating the regioselectivity in the singlet oxygen oxidation of substituted furans.

  DOI：

  10.1021/jo00025a012

文献信息

• Anti-inflammatory furanones
  申请人：Allergan, Inc.

  公开号：US05134128A1

  公开（公告）日：1992-07-28

  New 5-hydroxy-2-furanone compounds having anti-inflammatory, immunosuppressive and anti-proliferative activity and are useful in treating psoriasis and modifying calcium homeostasis.

  新的具有抗炎、免疫抑制和抗增殖活性的5-羟基-2-呋喃酮化合物对治疗牛皮癣和调节钙稳态具有用处。
• Singlet oxygen oxidation of substituted furans to 5-hydroxy-2(5H)-furanone
  作者：Gary C. M. Lee、Elizabeth T. Syage、Dale A. Harcourt、Judy M. Holmes、Michael E. Garst

  DOI：10.1021/jo00025a012

  日期：1991.12

  The conditions for the regiospecific singlet oxygen oxidation of various 2,4-disubstituted furans 9 to 4-substituted-2 (5H)-furanones 3 are developed. The presence of a C-2 substituent (e.g., trimethylsilyl, tert-butyldimethylsilyl, or tributylstannyl) in 9 is an absolute requirement for the formation of the 4-substituted-5-hydroxy-2(5H)-furanone regioisomer 3. When the C-2 substituent is triethylsilyl (TES) or TBDMS, however, apart from 3, the corresponding 5-trialkylsiloxy derivative 11 is also isolated in a significant amount. These silyl acetals are unexpectedly stable but can be hydrolyzed back to 3 on stirring with dilute acid. The formation of silyl acetals, to our knowledge, has never been reported in the singlet oxygen oxidation of (trialkylsilyl)furan. A plausible mechanism for their formation is proposed. The presence of a catalytic amount of water in the oxidation of 2-(trialkylsilyl)-4-substituted-furans not only eliminates the formation of the silyl acetals but also speeds up the rate of the oxidation process. Moreover, the oxidation can then be carried out at 0-degrees-C instead of at -78-degrees-C. Oxidation of 2-(1-hydroxyalkyl)-4-substituted-furans in the absence of a reducing agent gives little or no sign of 2,5-disubstituted-6-hydroxy-3(2H)-pyranone 23 but instead 26 selectively. Thus, the (1-hydroxy)alkyl group can be utilized as the trialkylsilyl or trialkylstannyl group in dictating the regioselectivity in the singlet oxygen oxidation of substituted furans.