5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone | 162920-92-5

• 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: 5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone
• 英文别名: 5,8-dimethoxy-1,4a-dimethyl-7-(1-methylethyl)-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone；5,8-dimethoxy-1,4a-dimethyl-7-propan-2-yl-3,4,9,10-tetrahydrophenanthren-2-one
• CAS: 162920-92-5
• 化学式: C₂₁H₂₈O₃
• 分子量: 328.452
• InChiKey: GXTWSNFFAHEUNE-UHFFFAOYSA-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：

  5,8-Dimethoxy-1,4a-dimethyl-7-isopropyl-4,4a,9,10-tetrahydro-2(3H)-phenanthrenone 在 palladium diacetate 1,1'-双(二苯基膦)二茂铁 、 三正丁胺 、 氨 、 甲基锂 、 lithium 、 三乙胺 、 叔丁醇 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 12.0h， 生成 (+)-(4aS,10aR)-Methyl 5,8-dimethoxy-1,4a-dimethyl-7-isopropyl-3,4,4a,9,10,10a-hexahydrophenanthrene-2-carboxylate
  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：

  2-Allyl-4-methoxy-6-isopropylphenol 在 氢氧化钾 、 sodium hydroxide 、 sodium chlorite 、 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 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醚 、 水 、 丙酮 、 苯 为溶剂， 反应 31.63h， 生成 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

• Method of treating a nitric oxide-associated disease with phenanthrene
  申请人：Otsuka Pharmaceutical Co., Ltd.

  公开号：US05654343A1

  公开（公告）日：1997-08-05

  This invention provides a nitric oxide synthesis inhibitor composition comprising, as an active ingredient, at least one member of the group consisting of various phenanthrene derivatives, typically represented by the following general formula (1), and salts thereof. ##STR1## The nitric oxide synthesis inhibitor composition of this invention is useful for the prophylaxis and therapy of nitric oxide-associated diseases such as endotoxin shock.

  这项发明提供一种一氧化氮合成抑制剂组合物，其活性成分至少包括各种菲类衍生物中的一种成员，通常由以下一般式（1）表示，并其盐。 这种发明的一氧化氮合成抑制剂组合物对于预防和治疗与一氧化氮相关的疾病，如内毒素休克，是有用的。
• NITROGEN MONOXIDE SYNTHESIS INHIBITOR
  申请人：OTSUKA PHARMACEUTICAL CO., LTD.

  公开号：EP0676196A1

  公开（公告）日：1995-10-11

  A nitrogen monoxide synthesis inhibitor containing as the active ingredient at least one member selected from phenanthrene derivatives represented by the compounds of general formula (1) and salts thereof; it is useful for preventing and treating various diseases caused by nitrogen monoxide, such as endotoxin shock.

  一种一氧化氮合成抑制剂，含有至少一种选自通式（1）化合物所代表的菲衍生物及其盐类的活性成分；可用于预防和治疗一氧化氮引起的各种疾病，如内毒素休克。
• Total synthesis of (±)-triptoquinone A
  作者：Kozo Shishido、Kiyoto Goto、Shizuka Miyoshi、Yoshihisa Takaishi、Masayuki Shibuya

  DOI：10.1016/s0040-4039(00)60582-8

  日期：1993.1

  A concise and practical total synthesis of (+/-)-triptoquinone A (1), a novel interleukin-1 inhibitor isolated from Tripterygium wilfordii var. regelii, has been achieved in 11 steps from the known naphthol 2.
• 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.
• JPH06263688A
  申请人：——

  公开号：JPH06263688A

  公开（公告）日：1994-09-20