tert-butyl (2-((1S,3S,3aS,3a1R,9aR)-1-((dimethylamino)oxy)-3-hydroxy-5-methoxy-1,3,3a,9a-tetrahydrophenanthro[4,5-bcd]furan-3a1(2H)-yl)ethyl)(methyl)carbamate | 1610613-40-5

• 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: tert-butyl (2-((1S,3S,3aS,3a1R,9aR)-1-((dimethylamino)oxy)-3-hydroxy-5-methoxy-1,3,3a,9a-tetrahydrophenanthro[4,5-bcd]furan-3a1(2H)-yl)ethyl)(methyl)carbamate
• CAS: 1610613-40-5
• 化学式: C₂₅H₃₆N₂O₆
• 分子量: 460.571
• InChiKey: CSDSRGVOCSRRAV-XPYSODJVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.22
• 重原子数：
  33.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  80.7
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (2-((1S,3S,3aS,3a1R,9aR)-1-((dimethylamino)oxy)-3-hydroxy-5-methoxy-1,3,3a,9a-tetrahydrophenanthro[4,5-bcd]furan-3a1(2H)-yl)ethyl)(methyl)carbamate 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 以10 mg的产率得到tert‐butyl (3‐((3S,3aS,3a1R)‐3‐((tert‐butyldimethylsilyl)oxy)‐5‐methoxy‐3,3a,3a1,9atetrahydrophenanthro[4,5‐bcd]furan‐3a1‐yl)ethyl)(methyl)carbamate
  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：

  2-[(5S,6R)-5-[(tert-butyldimethylsilyl)oxy]-6-hydroxycyclohex-1-en-1-yl]ethyl acetate 在 titanium(IV) isopropylate 、 三丁基膦 、 三叔丁基膦 、 偶氮二甲酸二异丙酯 、 四丁基氟化铵 、 potassium carbonate 、 戴斯-马丁氧化剂 、 三乙胺 、 N,N-二异丙基乙胺 、 三氟乙酸 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 59.67h， 生成 tert-butyl (2-((1S,3S,3aS,3a1R,9aR)-1-((dimethylamino)oxy)-3-hydroxy-5-methoxy-1,3,3a,9a-tetrahydrophenanthro[4,5-bcd]furan-3a1(2H)-yl)ethyl)(methyl)carbamate
  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