methyl (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-5-oxo-4,8-etheno-4H-indeno[5,6-d][1,3]dioxole-6-carboxylate | 914089-01-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-5-oxo-4,8-etheno-4H-indeno[5,6-d][1,3]dioxole-6-carboxylate
• 英文别名: methyl (1R,2R,6S,7S,8R,10S,12R)-1,4,4,10-tetramethyl-11-oxo-3,5-dioxatetracyclo[5.5.2.02,6.08,12]tetradec-13-ene-10-carboxylate
• CAS: 914089-01-3
• 化学式: C₁₈H₂₄O₅
• 分子量: 320.386
• InChiKey: FQXQKFKLTRNOSZ-ZXEPNJKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-5-oxo-4,8-etheno-4H-indeno[5,6-d][1,3]dioxole-6-carboxylate 在 盐酸 、 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 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 14.0h， 生成 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 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 methyl (3aR,4R,4aR,6S,7aR,8S,8aS)-3a,4a,5,6,7,7a,8,8a-octahydro-2,2,4,6-tetramethyl-5-oxo-4,8-etheno-4H-indeno[5,6-d][1,3]dioxole-6-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.