(1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6,7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3-ethanonaphthop[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate)

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6,7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3-ethanonaphthop[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate)
• 英文别名: [(1R,2S,4R,5R,8R,9S,10S,11R,13S)-13-(2,2-dimethylpropanoyloxy)-4-ethyl-6,14-dioxo-12,16-dioxapentacyclo[9.2.2.15,8.01,10.04,9]hexadecan-2-yl] 2,2-dimethylpropanoate
• 化学式: C₂₆H₃₆O₈
• 分子量: 476.567
• InChiKey: BKLRAWOJUHYUFC-YHCJMTTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  105
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6,7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3-ethanonaphthop[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate) 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 0.83h， 以78%的产率得到(1RS,3SR,3aRS,4SR,5aSR,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6,7,8,9,9a,9b-decahydro-9-hydroxy-7,10-dioxo-3H-1,3a-ethanonaphtho[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate)
  参考文献：
  名称：

  Stereoselective Synthesis of 5a-Ethyl-1,2,3,3a,4,5,5a,6,9a,9b-decahydro- 1,3,4-trihydroxy-3a-(hydroxymethyl)-7H-benz[e]inden-7-one Derivatives

  摘要：

  Homochiral Diels-Alder cyclodimerization of (+/-)-6-ethenyl-7-oxabicyclo[2.2.1]hept-5-en-2-endo-ol followed by oxidation gives (1RS,4RS,4aSR,4bSR,5RS,8RS,8aRS)-8a-ethenyl-1,3,4a,4b,5,6,8,8a,9-decahydro-11,4:5,8-diepoxyphenanthrene-2,7-dione (18). Selective hydrogenation followed by epoxidation produced (1RS,4RS,4aRS,5aRS,6aRS,7RS,10RS,10aSR,10bRS)-6a-ethyl-1,4,5a,6,6a,7,9,10,10a,10b-decahydro-1,4:7,10-di-epoxyphenanthro[8a,9b]oxirene-3,8-dione (21), which was solvolyzed (Me3SiOSO2CF3, Piv2O) with concomitant pinacol rearrangement involving an acyl-group migration to give a 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation intermediate, which finally generated (1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6, 7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3a-ethanonaphtho[1,2-c]furan-3.4-diyl bis(2,2-dimethylpropa noate) (24). Photo-reductive 7-oxa bridge opening of 24, followed by water elimination and silylation, provided (1RS,3SR,3aRS,4SR,5aSR,9aSR,9bSR)-7-{[(tert-butyl)dimethylsilyl]oxy}-5a-ethyl-1.4,5,5a,9a,9b-hexahydro-10-oxo-3H- 1,3-ethanonaphtho[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate) (34). Reduction of 34 with NaBH4 in MeOH followed by desilylation and alcohol protection produced (1RS,3RS,3aRS,4SR,5aSR,9aSR, 9bSR)-5a-ethyl-2,3,3a,4,5,5a,6,7,9a,9b-decahydro-1,3-bis(methoxymethoxy)-3a-[(methoxymethoxy)methyl]-7-oxo-1H-benz[e] inden-4-yl 2,2-dimethylpropanoate (5), a polyoxy-substituted decahydro-1H-benz[e]indene derivative with cis-transoid-trans junction for the two cyclohexane and the cyclopentane rings bearing an angular 3a-(oxymethyl) substituent.

  DOI：

  10.1002/(sici)1522-2675(19990908)82:9<1371::aid-hlca1371>3.0.co;2-n
• 作为产物：
  描述：

  三甲基乙酸酐 、 (1RS,4RS,4aRS,5aRS,6aRS,7RS,10RS,10aSR,10bRS)-6a-ethyl-1,4,5a,6,6a,7,9,10,10a,10b-decahydro-1,4:7,10-diepoxyphenanthro[8a,9-b]oxirene-3,8-dione 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 4.5h， 以54%的产率得到(1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6,7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3-ethanonaphthop[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate)
  参考文献：
  名称：

  Stereoselective Synthesis of 5a-Ethyl-1,2,3,3a,4,5,5a,6,9a,9b-decahydro- 1,3,4-trihydroxy-3a-(hydroxymethyl)-7H-benz[e]inden-7-one Derivatives

  摘要：

  Homochiral Diels-Alder cyclodimerization of (+/-)-6-ethenyl-7-oxabicyclo[2.2.1]hept-5-en-2-endo-ol followed by oxidation gives (1RS,4RS,4aSR,4bSR,5RS,8RS,8aRS)-8a-ethenyl-1,3,4a,4b,5,6,8,8a,9-decahydro-11,4:5,8-diepoxyphenanthrene-2,7-dione (18). Selective hydrogenation followed by epoxidation produced (1RS,4RS,4aRS,5aRS,6aRS,7RS,10RS,10aSR,10bRS)-6a-ethyl-1,4,5a,6,6a,7,9,10,10a,10b-decahydro-1,4:7,10-di-epoxyphenanthro[8a,9b]oxirene-3,8-dione (21), which was solvolyzed (Me3SiOSO2CF3, Piv2O) with concomitant pinacol rearrangement involving an acyl-group migration to give a 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation intermediate, which finally generated (1RS,3SR,3aRS,4SR,5aRS,6RS,9RS,9aSR,9bSR)-5a-ethyl-1,4,5,5a,6, 7,8,9,9a,9b-decahydro-7,10-dioxo-3H-6,9-epoxy-1,3a-ethanonaphtho[1,2-c]furan-3.4-diyl bis(2,2-dimethylpropa noate) (24). Photo-reductive 7-oxa bridge opening of 24, followed by water elimination and silylation, provided (1RS,3SR,3aRS,4SR,5aSR,9aSR,9bSR)-7-{[(tert-butyl)dimethylsilyl]oxy}-5a-ethyl-1.4,5,5a,9a,9b-hexahydro-10-oxo-3H- 1,3-ethanonaphtho[1,2-c]furan-3,4-diyl bis(2,2-dimethylpropanoate) (34). Reduction of 34 with NaBH4 in MeOH followed by desilylation and alcohol protection produced (1RS,3RS,3aRS,4SR,5aSR,9aSR, 9bSR)-5a-ethyl-2,3,3a,4,5,5a,6,7,9a,9b-decahydro-1,3-bis(methoxymethoxy)-3a-[(methoxymethoxy)methyl]-7-oxo-1H-benz[e] inden-4-yl 2,2-dimethylpropanoate (5), a polyoxy-substituted decahydro-1H-benz[e]indene derivative with cis-transoid-trans junction for the two cyclohexane and the cyclopentane rings bearing an angular 3a-(oxymethyl) substituent.

  DOI：

  10.1002/(sici)1522-2675(19990908)82:9<1371::aid-hlca1371>3.0.co;2-n