4-(hydroxymethyl)-3-methylene-5-pentyltetrahydrofuran-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 4-(hydroxymethyl)-3-methylene-5-pentyltetrahydrofuran-2-one
• 英文别名: 4-Hydroxymethyl-3-methylidene-5-pentyltetrahydrofuran-2-one；4-(Hydroxymethyl)-3-methylidene-5-pentyloxolan-2-one
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: IAKVDPBQACHUNY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(hydroxymethyl)-3-methylene-5-pentyltetrahydrofuran-2-one 在 jones reagent 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以80%的产率得到(2S)-4-亚甲基-5-氧代-2-戊基四氢呋喃-3-羧酸
  参考文献：
  名称：

  Stereoselective Synthesis of Polysubstituted Tetrahydrofurans by Radical Cyclization of Epoxides Using a Transition-Metal Radical Source. Application to the Total Synthesis of (±)-Methylenolactocin and (±)-Protolichesterinic Acid

  摘要：

  Radical cyclization reactions of substituted alpha-(prop-2-ynyloxy) epoxides using bis(cyclopentadienyl)-titanium(III) chloride as the radical source resulted in polysubstituted tetrahydrofurans. Titanium(III) species were prepared in situ from commercially available titanocene dichloride and zinc dust in tetrahydrofuran, Upon radical cyclization, 2-aryl epoxides 3a-e afforded only trans products 4a-e whereas the 2-alkyl epoxides 3f-h formed a mixture of isomeric products 4f-h in a ratio of 5:1. Some of the aryl tetrahydrofuran derivatives have already been used for the synthesis of bioactive furofuran lignans. 2-Pentyl-3-(hydroxymethyl)-4-methylenetetrahydrofuran (4f) and 2-tridecyl-3-(hydroxymethyl)-4-methylenetetrahydrofuran (4g) have been transformed to two antitumor antibiotics (+/-)-methylenolactocin (1f) and (+/-)-protolichesterinic acid (1g), respectively, in good overall yield.

  DOI：

  10.1021/jo971526d
• 作为产物：
  描述：

  1-辛烯-3-醇 在 重铬酸吡啶 、 bis(cyclopentadienyl)titanium (III) chloride 、 硫酸 、 4-甲基苯磺酸吡啶 、 sodium hydride 、 对甲苯磺酸 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 氯仿 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 生成 4-(hydroxymethyl)-3-methylene-5-pentyltetrahydrofuran-2-one
  参考文献：
  名称：

  Total synthesis of (±)-methylenolactocin by radical cyclisation of an epoxide using a transition-metal radical

  摘要：

  A stereoselective total synthesis of (+/-)-methylenotocin 1 is achieved via the radical cyclisation of an epoxide as a key step, using a titanium radical source.

  DOI：

  10.1039/p19960000403

文献信息

• Total synthesis of (±)-methylenolactocin by radical cyclisation of an epoxide using a transition-metal radical
  作者：Gourhari Maiti、Subhas Chandra Roy

  DOI：10.1039/p19960000403

  日期：——

  A stereoselective total synthesis of (+/-)-methylenotocin 1 is achieved via the radical cyclisation of an epoxide as a key step, using a titanium radical source.
• Stereoselective Synthesis of Polysubstituted Tetrahydrofurans by Radical Cyclization of Epoxides Using a Transition-Metal Radical Source. Application to the Total Synthesis of (±)-Methylenolactocin and (±)-Protolichesterinic Acid
  作者：Pijus Kumar Mandal、Gourhari Maiti、Subhas Chandra Roy

  DOI：10.1021/jo971526d

  日期：1998.5.1

  Radical cyclization reactions of substituted alpha-(prop-2-ynyloxy) epoxides using bis(cyclopentadienyl)-titanium(III) chloride as the radical source resulted in polysubstituted tetrahydrofurans. Titanium(III) species were prepared in situ from commercially available titanocene dichloride and zinc dust in tetrahydrofuran, Upon radical cyclization, 2-aryl epoxides 3a-e afforded only trans products 4a-e whereas the 2-alkyl epoxides 3f-h formed a mixture of isomeric products 4f-h in a ratio of 5:1. Some of the aryl tetrahydrofuran derivatives have already been used for the synthesis of bioactive furofuran lignans. 2-Pentyl-3-(hydroxymethyl)-4-methylenetetrahydrofuran (4f) and 2-tridecyl-3-(hydroxymethyl)-4-methylenetetrahydrofuran (4g) have been transformed to two antitumor antibiotics (+/-)-methylenolactocin (1f) and (+/-)-protolichesterinic acid (1g), respectively, in good overall yield.