(3R,4S,4aR,8R,8aS)-4-[(3aR,5S,6aS)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-5-yl]-8-ethenyl-8a-(hydroxymethyl)-3,4-dimethyl-3,4a,5,6,7,8-hexahydro-2H-naphthalen-1-one | 1027670-77-4

• 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: (3R,4S,4aR,8R,8aS)-4-[(3aR,5S,6aS)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-5-yl]-8-ethenyl-8a-(hydroxymethyl)-3,4-dimethyl-3,4a,5,6,7,8-hexahydro-2H-naphthalen-1-one
• CAS: 1027670-77-4
• 化学式: C₂₁H₃₂O₄
• 分子量: 348.483
• InChiKey: CEKFJLYZBITFNI-JHDMIENBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,4S,4aR,8R,8aS)-4-[(3aR,5S,6aS)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-5-yl]-8-ethenyl-8a-(hydroxymethyl)-3,4-dimethyl-3,4a,5,6,7,8-hexahydro-2H-naphthalen-1-one 在 咪唑 、 lithium aluminium tetrahydride 、 4-甲基苯磺酸吡啶 、 臭氧 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.5h， 生成 (4aS,6R,7S,7aR,11S,2'S,3a'R,6a'S)-7-(hexahydrofuro[2,3-b]furan-2'-yl)-3,3,6,7-tetramethyloctahydronaphtho[1,8a-d][1,3]dioxine-11-carbaldehyde
  参考文献：
  名称：

  Total Synthesis of Dihydroclerodin from (R)-(−)-Carvone

  摘要：

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.

  DOI：

  10.1021/jo991151r
• 作为产物：
  描述：

  (1S,2S,3R,2'S,3a'R,6a'S)-4-(4-(hexahydrofuro[2,3-b]furan-2'-yl)-2,3-dimethyl-5-oxocyclohexyl)butyraldehyde 在 copper(I) bromide dimethylsulfide complex 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 苯 为溶剂， 反应 5.17h， 生成 (3R,4S,4aR,8R,8aS)-4-[(3aR,5S,6aS)-2,3,3a,4,5,6a-hexahydrofuro[2,3-b]furan-5-yl]-8-ethenyl-8a-(hydroxymethyl)-3,4-dimethyl-3,4a,5,6,7,8-hexahydro-2H-naphthalen-1-one
  参考文献：
  名称：

  Total Synthesis of Dihydroclerodin from (R)-(−)-Carvone

  摘要：

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.

  DOI：

  10.1021/jo991151r

文献信息

• Total Synthesis of Dihydroclerodin from (<i>R</i>)-(−)-Carvone
  作者：Tommi M. Meulemans、Gerrit A. Stork、Fliur Z. Macaev、Ben J. M. Jansen、Aede de Groot

  DOI：10.1021/jo991151r

  日期：1999.12.1

  The first total synthesis of the natural enantiomer of the insect-antifeedant dihydroclerodin (1) and lupulin C (40) has been achieved starting from (R)-(-)-carvone (2). In the applied strategy, the hexahydrofuro[2,3-b]furan moiety was introduced in an early stage of the synthesis. The correct configuration at C-9, C-11, C-13, and C-16 was established by application of a remarkably diastereoselective Mukaiyama reaction. The desired configuration at C-10 was obtained by catalytic reduction of the intermediate enone 21. After annulation of the second ring, the structural features at C-4, C-5, and C-6 were introduced. The successful finishing of the synthesis included a Chugaev elimination to give the exocyclic double bond at C-4 that is present in lupulin C. Oxidation of this double bond with m-CPBA afforded dihydroclerodin.