(6R,9S,13R,14S)-7,8-Didehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,7-dimethoxymorphinan-6-ol | 164738-86-7

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 吗啡烷
• 英文名称: (6R,9S,13R,14S)-7,8-Didehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,7-dimethoxymorphinan-6-ol
• CAS: 164738-86-7
• 化学式: C₃₃H₃₅NO₆
• 分子量: 541.644
• InChiKey: WPHXCDCTGVZCRL-GLPSKGHJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  40.0
• 可旋转键数：
  7.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  77.46
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (6R,9S,13R,14S)-7,8-Didehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,7-dimethoxymorphinan-6-ol 在 palladium dihydroxide 作用下， 以 乙醇 、 环己烯 为溶剂， 反应 0.75h， 以88%的产率得到(6R,9S,13R,14S)-7,8-Didehydro-4-hydroxy-3,7-dimethoxymorphinan-6-ol
  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
• 作为产物：
  描述：

  (9S,13R,14S)-7,8-Dehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,7-dimethoxymorphinan-6-one 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以50%的产率得到(6S,9S,13R,14S)-7,8-Didehydro-4-(benzyloxy)-17-<(benzyloxy)carbonyl>-3,7-dimethoxymorphinan-6-ol
  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

• Synthesis of an antitumour alkaloid sinococuline from sinomenine
  作者：Yukio Hitotsuyanagi、Hiroshi Ikuta、Kunihiko Nishimura、Koichi Takeya、Hideji Itokawa

  DOI：10.1039/c39940002707

  日期：——

  An antitumour morphinane alkaloid sinococuline 1 is synthesised from sinomenine 2 in an efficient manner.

  抗肿瘤吗啡烯生物碱辛可可林1是通过高效的方式从辛伐美辛2合成的。