5-(furan-3-yl)-8a'-methoxy-7'-methyl-3',4,5,5',5a',7',8',8a'-octahydro-2H-spiro[furan-3,6'-naphtho[1,8-bc]furan]-2,2'(4'H)-dione | 136176-65-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 5-(furan-3-yl)-8a'-methoxy-7'-methyl-3',4,5,5',5a',7',8',8a'-octahydro-2H-spiro[furan-3,6'-naphtho[1,8-bc]furan]-2,2'(4'H)-dione
• 英文别名: (12S)-15,16-epoxy-6β-methoxy-19-norneoclerodane-4,13-(16),14-triene-18,6α;20,12-diolide；(12S)-15,16-Epoxy-6β-methoxy-19-norneoclerodane-4,13(16),14-triene-18,6α,20,12-diolide
• CAS: 136176-65-3
• 化学式: C₂₀H₂₂O₆
• 分子量: 358.391
• InChiKey: JEVGBBFQRUXXBJ-GPHYKJPNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  74.97
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  5-(furan-3-yl)-7'-methyl-2'-oxo-2',3',4,4',5,5',5a',7'-octahydro-2H-spiro[furan-3,6'-naphtho[1,8-bc]furan]-2-yl acetate 在 chromium trioxide-pyridine complex 、 硫酸 、 potassium carbonate 作用下， 反应 4.5h， 生成 5-(furan-3-yl)-8a'-methoxy-7'-methyl-3',4,5,5',5a',7',8',8a'-octahydro-2H-spiro[furan-3,6'-naphtho[1,8-bc]furan]-2,2'(4'H)-dione
  参考文献：
  名称：

  Transformation of neoclerodane diterpenoids into 19-norneoclerodane derivatives

  摘要：

  The neoclerodane diterpenoid eriocephalin (1) was transformed into its 19-nor derivatives 3 and 4 by reaction with potassium tert-butoxide in THF, whereas with the same treatment compound 6 yielded only the transacetylation derivative 7. These results indicated that 19-acetoxy-4-alpha,18-epoxy-7-alpha-hydroxy-6-oxoneoclerodane derivatives are transformed into the corresponding 19-nor compounds in a retroaldol reaction by loss of the C-19 carbon as formaldehyde followed by opening of the oxirane ring and intramolecular attack by a C-18 alkoxide on the carbonyl C-6 carbon atom, giving the allylic hemiacetal 3, which is easily dehydrated to the furanic derivative 4. Compound 4 was transformed into the alpha,beta-unsaturated gamma,delta-enol gamma-lactone 8 by an oxidation reaction with atomspheric oxygen in chloroform solution. Alternatively, it gave the alpha,beta-unsaturated gamma-lactone 11 under acid catalysis. These reactions allowed the partial syntheses of the naturally occurring diterpenoids teuscorolide (9) and teucvin (12) and are of interest for chemical transformations of substances of this kind.

  DOI：

  10.1021/jo00023a027

文献信息

• Transformation of neoclerodane diterpenoids into 19-norneoclerodane derivatives
  作者：Gema Dominguez、Maria C. De la Torre、Benjamin Rodriguez

  DOI：10.1021/jo00023a027

  日期：1991.11

  The neoclerodane diterpenoid eriocephalin (1) was transformed into its 19-nor derivatives 3 and 4 by reaction with potassium tert-butoxide in THF, whereas with the same treatment compound 6 yielded only the transacetylation derivative 7. These results indicated that 19-acetoxy-4-alpha,18-epoxy-7-alpha-hydroxy-6-oxoneoclerodane derivatives are transformed into the corresponding 19-nor compounds in a retroaldol reaction by loss of the C-19 carbon as formaldehyde followed by opening of the oxirane ring and intramolecular attack by a C-18 alkoxide on the carbonyl C-6 carbon atom, giving the allylic hemiacetal 3, which is easily dehydrated to the furanic derivative 4. Compound 4 was transformed into the alpha,beta-unsaturated gamma,delta-enol gamma-lactone 8 by an oxidation reaction with atomspheric oxygen in chloroform solution. Alternatively, it gave the alpha,beta-unsaturated gamma-lactone 11 under acid catalysis. These reactions allowed the partial syntheses of the naturally occurring diterpenoids teuscorolide (9) and teucvin (12) and are of interest for chemical transformations of substances of this kind.