7-epi-Sinococuline

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 7-epi-Sinococuline
• 英文别名: (1S,9S,12R,13S)-4,11-dimethoxy-17-azatetracyclo[7.5.3.01,10.02,7]heptadeca-2(7),3,5,10-tetraene-3,12,13-triol
• 化学式: C₁₈H₂₃NO₅
• 分子量: 333.384
• InChiKey: MFKPWBJXKCSPGK-FWRUBQMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  91.2
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (6S,7R,9S,13S)-8,14-Didehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,8-dimethoxymorphinane-6,7-diol 在 palladium dihydroxide 作用下， 以 乙醇 、 环己烯 为溶剂， 反应 1.0h， 以98%的产率得到7-epi-Sinococuline
  参考文献：
  名称：

  Syntheses of Antitumor Morphinane Alkaloids, Sinococuline and 6-epi-, 7-epi-, and 6-epi-7-epi-Sinococuline, from Sinomenine

  摘要：

  An antitumor alkaloid, sinococuline (1), and its C-6 and/or C-7 epimeric analogs 3-5 have been synthesized from sinomenine (2). The carbonyl transposition from 9 to 8 using selenoxide chemistry proceeded in an efficient manner. Successive C-6 hydroxylation through the potassium enolate oxidation with (-)-(2S,8aR)-(camphorsulfonyl)oxaziridine (23) predominantly produced the beta-hydroxy enone 7a, which allowed access to sinococuline (1) and the 7-epi-analog 4. On the contrary, the oxidation of the lithium enolate with (+/-)-trans-2-(phenylsulfonyl)-3-phenyloxaziridine (22) resulted in predominant formation of the a-hydroxy enone 7b, which was converted to the 6-epi-analogs 3 and 5. In contrast to the marked antitumor activity of 1, analogs 3-5 showed no activity.

  DOI：

  10.1021/jo00119a037

文献信息

• Syntheses of Antitumor Morphinane Alkaloids, Sinococuline and 6-epi-, 7-epi-, and 6-epi-7-epi-Sinococuline, from Sinomenine
  作者：Yukio Hitotsuyanagi、Kunihiko Nishimura、Hiroshi Ikuta、Koichi Takeya、Hideji Itokawa

  DOI：10.1021/jo00119a037

  日期：1995.7

  An antitumor alkaloid, sinococuline (1), and its C-6 and/or C-7 epimeric analogs 3-5 have been synthesized from sinomenine (2). The carbonyl transposition from 9 to 8 using selenoxide chemistry proceeded in an efficient manner. Successive C-6 hydroxylation through the potassium enolate oxidation with (-)-(2S,8aR)-(camphorsulfonyl)oxaziridine (23) predominantly produced the beta-hydroxy enone 7a, which allowed access to sinococuline (1) and the 7-epi-analog 4. On the contrary, the oxidation of the lithium enolate with (+/-)-trans-2-(phenylsulfonyl)-3-phenyloxaziridine (22) resulted in predominant formation of the a-hydroxy enone 7b, which was converted to the 6-epi-analogs 3 and 5. In contrast to the marked antitumor activity of 1, analogs 3-5 showed no activity.