(+)-(4aS)-5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone | 155320-93-7

• 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: (+)-(4aS)-5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone
• 英文别名: (4aS)-5,8-dimethoxy-1,4a-dimethyl-7-propan-2-yl-3,4,9,10-tetrahydrophenanthren-2-one
• CAS: 155320-93-7
• 化学式: C₂₁H₂₈O₃
• 分子量: 328.452
• InChiKey: GXTWSNFFAHEUNE-NRFANRHFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(4aS)-5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone 在 氨 、 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以3%的产率得到(+)-(1S,4aS,10aR)-3,4,4a,9,10,10a-Hexahydro-1,4a-dimethyl-5,8-dimethoxy-7-isopropyl-2(1H)-phenanthrenone
  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 (-)-N-(p-trifluoromethyl)benzylcinchonidinium bromide 氢氧化钾 、 sodium hydroxide 、 sodium chlorite 、 copper(l) iodide 、 草酰氯 、 18-冠醚-6 、 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 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 70.63h， 生成 (+)-(4aS)-5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone
  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

• Enantiocontrolled total synthesis of the diterpenoids, triptoquinone B, C and triptocallol
  作者：Itsuki Yamamura、Yoko Fujiwara、Toshihiro Yamato、Osamu Irie、Kozo Shishido

  DOI：10.1016/s0040-4039(97)00841-1

  日期：1997.6

  An efficient and enantiocontrolled synthesis of triptoquinone B and C, which possess interleukin-1 inhibitory activity, has been accomplished employing the lipase-catalyzed kinetic resolution and a highly diastereoselective radical cyclization as key synthetic steps. In addition, the first total synthesis of triptocallol has been achieved utilizing the same strategy. (C) 1997 Elsevier Science Ltd.