2-Hydroxy-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2-(1-methoxy-1-(diphenylphosphoryl)methyl)-2,3,4,4a,9,10-hexahydrophenanthrene | 153341-07-2

• 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: 2-Hydroxy-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2-(1-methoxy-1-(diphenylphosphoryl)methyl)-2,3,4,4a,9,10-hexahydrophenanthrene
• 英文别名: 2-Hydroxy-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2-[1-methoxy-1-(diphenylphosphoryl)methyl]-2,3,4,4a,9,10-hexahydrophenanthrene；2-[Diphenylphosphoryl(methoxy)methyl]-5,8-dimethoxy-1,4a-dimethyl-7-propan-2-yl-3,4,9,10-tetrahydrophenanthren-2-ol
• CAS: 153341-07-2
• 化学式: C₃₅H₄₃O₅P
• 分子量: 574.697
• InChiKey: RUZKCLSGDCSMRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  41
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Hydroxy-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2-(1-methoxy-1-(diphenylphosphoryl)methyl)-2,3,4,4a,9,10-hexahydrophenanthrene 在 potassium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 (Z)-2-(Methoxymethylene)-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2,3,4,4a,9,10-hexahydrophenanthrene 、 (E)-2-(Methoxymethylene)-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2,3,4,4a,9,10-hexahydrophenanthrene
  参考文献：
  名称：

  Synthetic studies on diterpenoid quinones with interleukin-1 inhibitory activity. Total synthesis of (.+-.)- and (+)-triptoquinone A

  摘要：

  An efficient first total synthesis of (+/-)- and (+)-triptoquinone A (1), a novel diterpenoid quinone with significant inhibitory activity against interleukin-1 releases, has been completed. Birch reduction of tricyclic enone (+/-)-7, prepared from known 6-methoxy-2-isopropyl-1-naphthol (22), which is readily available in large quantities, was followed by immediate enolate trapping to provide silyl enol ether (+/-)-30. Compound 30 was converted into carboxylic acid (+/-)-4 via the corresponding enol triflate (+/-)-31 either by sequential palladium-catalyzed carbonylation and oxidation or by direct carboxylation. The total synthesis of (+/-)-1 was completed by oxidation of (+/-)-4 with CAN in 12 steps from 22 in 19% overall yield at best. A second, enantioselective total synthesis of (+)-1 was accomplished via (+/-)-7, which was prepared by (-)-N- [4-(trifluoromethyl)benzyl]cinchonidinium bromide (33) catalyzed asymmetric Michael reaction of 6 with ethyl vinyl ketone and a subsequent aldol condensation. The absolute structures of triptoquinone B (2) and C (3), which were isolated concomitantly with triptoquinone A from the same plant sources, were established by a series of chemical reactions based on (+)-7.

  DOI：

  10.1021/jo00081a021
• 作为产物：
  描述：

  4-溴-2-异丙基苯酚 在 氢氧化钾 、 sodium hydroxide 、 sodium chlorite 、 copper(l) iodide 、 草酰氯 、 dimethyl sulfide borane 、 氨基磺酸 、 双氧水 、 potassium carbonate 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 48.55h， 生成 2-Hydroxy-5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-2-(1-methoxy-1-(diphenylphosphoryl)methyl)-2,3,4,4a,9,10-hexahydrophenanthrene
  参考文献：
  名称：

  Synthetic studies on diterpenoid quinones with interleukin-1 inhibitory activity. Total synthesis of (.+-.)- and (+)-triptoquinone A

  摘要：

  An efficient first total synthesis of (+/-)- and (+)-triptoquinone A (1), a novel diterpenoid quinone with significant inhibitory activity against interleukin-1 releases, has been completed. Birch reduction of tricyclic enone (+/-)-7, prepared from known 6-methoxy-2-isopropyl-1-naphthol (22), which is readily available in large quantities, was followed by immediate enolate trapping to provide silyl enol ether (+/-)-30. Compound 30 was converted into carboxylic acid (+/-)-4 via the corresponding enol triflate (+/-)-31 either by sequential palladium-catalyzed carbonylation and oxidation or by direct carboxylation. The total synthesis of (+/-)-1 was completed by oxidation of (+/-)-4 with CAN in 12 steps from 22 in 19% overall yield at best. A second, enantioselective total synthesis of (+)-1 was accomplished via (+/-)-7, which was prepared by (-)-N- [4-(trifluoromethyl)benzyl]cinchonidinium bromide (33) catalyzed asymmetric Michael reaction of 6 with ethyl vinyl ketone and a subsequent aldol condensation. The absolute structures of triptoquinone B (2) and C (3), which were isolated concomitantly with triptoquinone A from the same plant sources, were established by a series of chemical reactions based on (+)-7.

  DOI：

  10.1021/jo00081a021

文献信息

• Synthetic studies on diterpenoid quinones with interleukin-1 inhibitory activity. Total synthesis of (.+-.)- and (+)-triptoquinone A
  作者：Kozo Shishido、Kiyoto Goto、Shizuka Miyoshi、Yoshihisa Takaishi、Masayuki Shibuya

  DOI：10.1021/jo00081a021

  日期：1994.1

  An efficient first total synthesis of (+/-)- and (+)-triptoquinone A (1), a novel diterpenoid quinone with significant inhibitory activity against interleukin-1 releases, has been completed. Birch reduction of tricyclic enone (+/-)-7, prepared from known 6-methoxy-2-isopropyl-1-naphthol (22), which is readily available in large quantities, was followed by immediate enolate trapping to provide silyl enol ether (+/-)-30. Compound 30 was converted into carboxylic acid (+/-)-4 via the corresponding enol triflate (+/-)-31 either by sequential palladium-catalyzed carbonylation and oxidation or by direct carboxylation. The total synthesis of (+/-)-1 was completed by oxidation of (+/-)-4 with CAN in 12 steps from 22 in 19% overall yield at best. A second, enantioselective total synthesis of (+)-1 was accomplished via (+/-)-7, which was prepared by (-)-N- [4-(trifluoromethyl)benzyl]cinchonidinium bromide (33) catalyzed asymmetric Michael reaction of 6 with ethyl vinyl ketone and a subsequent aldol condensation. The absolute structures of triptoquinone B (2) and C (3), which were isolated concomitantly with triptoquinone A from the same plant sources, were established by a series of chemical reactions based on (+)-7.