methyl (2S,3aR,4R,7S,7aS,9R)-9-(benzoyloxy)-2,3,3a,4,7,7a-hexahydro-2,4-dimethyl-8-oxo-4,7-ethano-1H-indene-2-carboxylate | 914089-11-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (2S,3aR,4R,7S,7aS,9R)-9-(benzoyloxy)-2,3,3a,4,7,7a-hexahydro-2,4-dimethyl-8-oxo-4,7-ethano-1H-indene-2-carboxylate
• 英文别名: methyl (1R,2R,4S,6S,7S,10R)-10-benzoyloxy-1,4-dimethyl-11-oxotricyclo[5.2.2.02,6]undec-8-ene-4-carboxylate
• CAS: 914089-11-5
• 化学式: C₂₂H₂₄O₅
• 分子量: 368.43
• InChiKey: ZMHRGOFXZBQSAL-CJMUYKIVSA-N

物化性质

• 沸点：
  473.8±45.0 °C(predicted)
• 密度：
  1.24±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (2S,3aR,4R,7S,7aS,9R)-9-(benzoyloxy)-2,3,3a,4,7,7a-hexahydro-2,4-dimethyl-8-oxo-4,7-ethano-1H-indene-2-carboxylate 在 苯乙酮 作用下， 以 丙酮 为溶剂， 反应 80.0h， 以82%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
• 作为产物：
  描述：

  (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-4,8-etheno-5H-indeno[5,6-d][1,3]dioxol-5-one 在 盐酸 、 4-二甲氨基吡啶 、 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl 、 sodium tetrahydroborate 、 cerium(III) chloride 、 偶氮二异丁腈 、 Dowex-50 、 三正丁基氢锡 、 sodium hexamethyldisilazane 、 对甲苯磺酸 、 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 18.0h， 生成 methyl (2S,3aR,4R,7S,7aS,9R)-9-(benzoyloxy)-2,3,3a,4,7,7a-hexahydro-2,4-dimethyl-8-oxo-4,7-ethano-1H-indene-2-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

文献信息

• Chemoenzymatic total syntheses of the linear triquinane-type natural products (+)-hirsutic acid and (−)-complicatic acid from toluene
  作者：Martin G. Banwell、Kerrie A.B. Austin、Anthony C. Willis

  DOI：10.1016/j.tet.2007.03.073

  日期：2007.7

  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.