17β-acetoxy-3-methoxy-14,17α-ethenooestra-1,3,5(10)-triene-16α-carbaldahyde | 130535-89-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 17β-acetoxy-3-methoxy-14,17α-ethenooestra-1,3,5(10)-triene-16α-carbaldahyde
• 英文别名: [(1R,2R,11S,14S,15S,19R)-19-formyl-7-methoxy-14-methyl-15-pentacyclo[13.2.2.01,14.02,11.05,10]nonadeca-5(10),6,8,16-tetraenyl] acetate
• CAS: 130535-89-6
• 化学式: C₂₄H₂₈O₄
• 分子量: 380.484
• InChiKey: IRHAGWNIOSLUFZ-GSVDHGKISA-N

物化性质

• 沸点：
  504.3±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  17β-acetoxy-3-methoxy-14,17α-ethenooestra-1,3,5(10)-triene-16α-carbaldahyde 在 10% palladium on active carbon 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 1.5h， 以97%的产率得到17β-acetoxy-3-methoxy-14,17α-ethenoestra-1,3,5(10)-triene-16α-carbaldehyde
  参考文献：
  名称：

  Cycloaddition-fragmentation route to 14β-allylestrone and the derived 14α,17α-ethano analogue of estriol

  摘要：

  3-Methoxyestra-1,3,5(10),14,16-pentaen-17-yl acetate (1) undergoes efficient baron trifluoride catalysed cycloaddition at 20 degrees C with. acrolein to give the corresponding 17 beta-acetoxy 14 alpha,17 alpha-etheno 16 alpha-carbaldebyde (2). The derived 16 alpha-tosyloxymethyl intermediates are converted via Wharton fragmentation into 14 beta-allyl derivatives of estrone. Oxidative cleavage of 14-allyl-3-methoxy-14 beta-estra-1,3,5(10)-trien-17-one (14) furnishes the 14 beta-formylmethyl derivative (17). Intramolecular reductive cyclisation of 17, followed by stepwise protection-deprotection of functionality provides an efficient synthetic route to 14,17 alpha-ethanoestra-1,3,5(10)-triene-3,16 alpha,17 beta-triol (23), the structure of which is confirmed with the aid of X-ray crystallographic analysis of the derived triacetate.

  DOI：

  10.1016/s0040-4020(01)80653-0
• 作为产物：
  描述：

  17-acetyloxy-3-methoxyestra-1,3,5(10),14,16-pentaene 、 丙烯醛 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 22.0h， 以83%的产率得到17β-acetoxy-3-methoxy-14,17α-ethenooestra-1,3,5(10)-triene-16α-carbaldahyde
  参考文献：
  名称：

  Cycloaddition-fragmentation route to 14β-allylestrone and the derived 14α,17α-ethano analogue of estriol

  摘要：

  3-Methoxyestra-1,3,5(10),14,16-pentaen-17-yl acetate (1) undergoes efficient baron trifluoride catalysed cycloaddition at 20 degrees C with. acrolein to give the corresponding 17 beta-acetoxy 14 alpha,17 alpha-etheno 16 alpha-carbaldebyde (2). The derived 16 alpha-tosyloxymethyl intermediates are converted via Wharton fragmentation into 14 beta-allyl derivatives of estrone. Oxidative cleavage of 14-allyl-3-methoxy-14 beta-estra-1,3,5(10)-trien-17-one (14) furnishes the 14 beta-formylmethyl derivative (17). Intramolecular reductive cyclisation of 17, followed by stepwise protection-deprotection of functionality provides an efficient synthetic route to 14,17 alpha-ethanoestra-1,3,5(10)-triene-3,16 alpha,17 beta-triol (23), the structure of which is confirmed with the aid of X-ray crystallographic analysis of the derived triacetate.

  DOI：

  10.1016/s0040-4020(01)80653-0

文献信息

• Cycloaddition-mediated strategies for synthesis of perhydrobenzo[14,15]-14β-19-norsteroids
  作者：James R. Bull、Eugene S. Sickle

  DOI：10.1039/b005129m

  日期：——

  Methods are described for sequential cycloaddition–fragmentation–recombination and cycloaddition–rearrangement-mediated processes for synthesis of the title compounds. Reaction of methyl vinyl ketone with 3-methoxyestra-1,3,5(10),14,16-pentaen-17-yl acetate 1 gives a cycloadduct 2, which undergoes retroaldol cleavage followed by intramolecular Michael reaction, to generate 3-methoxy-5′,6′-dihydro-15αH-benzo[14

  描述了依次加成-片段化-重组和环加成的方法。 环加成–重组介导的标题化合物的合成过程。的反应甲基乙烯基酮用3-甲氧基estra-1,3,5（10），14,16-戊烯-17-乙酸酯 1得到环加 合物2，其进行逆醛醇裂解，随后进行分子内迈克尔反应，生成3-甲氧基-5'，6 ' -二氢15α ħ -苯并[14,15]-14β -雌-1,3,5（10） -三烯-4'（3' ħ），17-二酮 4。类似地，表明各种16α-烯基-14α，17α-炔雌醇会进行现成的[3,3]-σ重排，从而产生该五环系统的功能变体。合成新的（过氢苯并）[14,15]-14β-类似物的途径雌二醇 进行了描述，并概述了从替代分子内反应途径衍生出的14β，16β-propane-19-norsteroids的化学方面。