2-((3S,3aS,3a1R,9aR)-3-((tert-butyldimethylsilyl)oxy)-5-methoxy-1,2,3,3a,3a1,9ahexahydrophenanthro[4,5-bcd]furan-3a-1-yl)ethanol | 1610613-47-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-((3S,3aS,3a1R,9aR)-3-((tert-butyldimethylsilyl)oxy)-5-methoxy-1,2,3,3a,3a1,9ahexahydrophenanthro[4,5-bcd]furan-3a-1-yl)ethanol
• CAS: 1610613-47-2
• 化学式: C₂₃H₃₄O₄Si
• 分子量: 402.606
• InChiKey: LFKOABRHJHPEEB-JOXJFCDYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-((3S,3aS,3a1R,9aR)-3-((tert-butyldimethylsilyl)oxy)-5-methoxy-1,2,3,3a,3a1,9ahexahydrophenanthro[4,5-bcd]furan-3a-1-yl)ethanol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以72%的产率得到2-((3S,3aS,3a1R,9aR)-3-((tert-butyldimethylsilyl)oxy)-5-methoxy-1,2,3,3a,3a1,9ahexahydrophenanthro[4,5-bcd]furan-3a-1-yl)acetaldehyde
  参考文献：
  名称：

  通过硝基环加成和/或自由基环化实现对可待因和其他吗啡类的化学酶式正式全合成。C-9 / C-14立体中心的控制策略比较

  摘要：

  AbstractFormal total syntheses of ent‐codeine and other morphinans were accomplished from 1‐phenyl‐2‐acetoxyethane, which was subjected to enzymatic dihydroxylation by toluene dioxygenase overexpressed in Eschericia coli JM109 (pDTG601A). The resulting cis‐dihydroarenediol was coupled with a phenol derived from bromoisovanillin and a subsequent Heck reaction was used to establish the C‐13 quaternary center. Two strategies were employed to set the C‐14 center: nitrone and nitrile oxide cycloadditions to the C‐8/C‐14 olefin and a radical cyclization of an aldehyde to C‐14. Both strategies yielded tetracyclic products that were converted to known intermediates for the synthesis of ent‐codeine, ent‐codeinone, and ent‐hydrocodone. Experimental and spectral data are provided for all new compounds.magnified image

  DOI：

  10.1002/adsc.201400016
• 作为产物：
  描述：

  在 sodium hydroxide 作用下， 以 乙醇 、 水 为溶剂， 反应 1.0h， 以15 mg的产率得到2-((3S,3aS,3a1R,9aR)-3-((tert-butyldimethylsilyl)oxy)-5-methoxy-1,2,3,3a,3a1,9ahexahydrophenanthro[4,5-bcd]furan-3a-1-yl)ethanol
  参考文献：
  名称：

  通过硝基环加成和/或自由基环化实现对可待因和其他吗啡类的化学酶式正式全合成。C-9 / C-14立体中心的控制策略比较

  摘要：

  AbstractFormal total syntheses of ent‐codeine and other morphinans were accomplished from 1‐phenyl‐2‐acetoxyethane, which was subjected to enzymatic dihydroxylation by toluene dioxygenase overexpressed in Eschericia coli JM109 (pDTG601A). The resulting cis‐dihydroarenediol was coupled with a phenol derived from bromoisovanillin and a subsequent Heck reaction was used to establish the C‐13 quaternary center. Two strategies were employed to set the C‐14 center: nitrone and nitrile oxide cycloadditions to the C‐8/C‐14 olefin and a radical cyclization of an aldehyde to C‐14. Both strategies yielded tetracyclic products that were converted to known intermediates for the synthesis of ent‐codeine, ent‐codeinone, and ent‐hydrocodone. Experimental and spectral data are provided for all new compounds.magnified image

  DOI：

  10.1002/adsc.201400016