methyl (1S,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate | 914089-12-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: methyl (1S,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate
• CAS: 914089-12-6
• 化学式: C₂₂H₂₄O₅
• 分子量: 368.43
• InChiKey: GRDUMUUZMWFXCB-LGEQMQQYSA-N

物化性质

• 沸点：
  472.9±45.0 °C(predicted)
• 密度：
  1.29±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  27.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  69.67
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  methyl (1S,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate 在 aluminum oxide 、 samarium diiodide 、 对甲苯磺酸 、 lithium hexamethyldisilazane 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 二甲基亚砜 、 甲苯 为溶剂， 反应 89.5h， 生成 methyl (1S,2R,4S,6S)-1,4-dimethyl-11-methylene-10-oxotricyclo<6.3.0.0^2,6>undec-8-ene-5-carboxylate
  参考文献：
  名称：

  Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (−)-complicatic acid from toluene

  摘要：

  Total syntheses of title natural products, 1 and 2, have been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered micro-organism Escherichia coli JM109 (pDTG601) that over-expresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in these syntheses, the first of which was a high-pressure- promoted Diels-Alder cycloaddition reaction between diene 8 and cyclopentenone to give adduct 9. The second key step was the photochemically promoted oxa-di-pi-methane rearrangement of the bicyclo[2.2.2] octenone derivative, 18, of 9 to give 20 while the third key step was the reductive cleavage of the last compound so as to afford the linear triquinane 22. Elaboration of compound 22 to targets 1 and 2 followed conventional and/or established procedures. Single-crystal X-ray analyses were carried out on compounds 10-13, 15, 18, 24, and 34. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.073
• 作为产物：
  描述：

  methyl (1R,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate 在 苯乙酮 作用下， 以 丙酮 为溶剂， 反应 36.0h， 以97%的产率得到methyl (1S,2aR,2bR,2cR,4S,5aR,5bS,5cS)-1-(benzoyloxy)-decahydro-4,5b-dimethyl-2-oxo-1H-cyclopenta[a]cyclopropa[cd]pentalene-4-carboxylate
  参考文献：
  名称：

  Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (−)-complicatic acid from toluene

  摘要：

  Total syntheses of title natural products, 1 and 2, have been achieved using the cis-1,2-dihydrocatechol 7 as starting material. Compound 7 is readily obtained in large quantity and enantiomerically pure form through the whole-cell biotransformation of toluene using the genetically engineered micro-organism Escherichia coli JM109 (pDTG601) that over-expresses the enzyme toluene dioxygenase (TDO). Three key chemical steps were employed in these syntheses, the first of which was a high-pressure- promoted Diels-Alder cycloaddition reaction between diene 8 and cyclopentenone to give adduct 9. The second key step was the photochemically promoted oxa-di-pi-methane rearrangement of the bicyclo[2.2.2] octenone derivative, 18, of 9 to give 20 while the third key step was the reductive cleavage of the last compound so as to afford the linear triquinane 22. Elaboration of compound 22 to targets 1 and 2 followed conventional and/or established procedures. Single-crystal X-ray analyses were carried out on compounds 10-13, 15, 18, 24, and 34. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.03.073