methyl (2S,3aR,4R,7S,7aS,8S,9R)-2,3,3a,4,7,7a-hexahydro-8,9-dihydroxy-2,4-dimethyl-4,7-ethano-1H-indene-2-carboxylate | 914089-08-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl (2S,3aR,4R,7S,7aS,8S,9R)-2,3,3a,4,7,7a-hexahydro-8,9-dihydroxy-2,4-dimethyl-4,7-ethano-1H-indene-2-carboxylate
• 英文别名: methyl (1R,2R,4S,6S,7S,10R,11S)-10,11-dihydroxy-1,4-dimethyltricyclo[5.2.2.02,6]undec-8-ene-4-carboxylate
• CAS: 914089-08-0
• 化学式: C₁₅H₂₂O₄
• 分子量: 266.337
• InChiKey: BMFCXSRBEYIIMS-IRKGCBOHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (2S,3aR,4R,7S,7aS,8S,9R)-2,3,3a,4,7,7a-hexahydro-8,9-dihydroxy-2,4-dimethyl-4,7-ethano-1H-indene-2-carboxylate 在 4-acetylamino-2,2,6,6-tetramethylpiperidine-N-oxyl 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 以882 mg的产率得到methyl (2S,3aR,4R,7S,7aS,9R)-2,3,3a,4,7,7a-hexahydro-9-hydroxy-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
• 作为产物：
  描述：

  (3aR,4R,4aR,7aR,8S,8aS)-3a,4,4a,6,7,7a,8,8a-octahydro-2,2,4-trimethyl-4,8-etheno-5H-indeno[5,6-d]-1,3-dioxol-5-one 在 盐酸 、 sodium tetrahydroborate 、 cerium(III) chloride 、 偶氮二异丁腈 、 Dowex-50 、 三正丁基氢锡 、 sodium hexamethyldisilazane 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 水 、 甲苯 为溶剂， 反应 22.0h， 生成 methyl (2S,3aR,4R,7S,7aS,8S,9R)-2,3,3a,4,7,7a-hexahydro-8,9-dihydroxy-2,4-dimethyl-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