(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 | 254752-96-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 呋喃类
• 英文名称: (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
• CAS: 254752-96-0
• 化学式: C₂₃H₃₆O₅
• 分子量: 392.536
• InChiKey: KYYBCQQNIFGUQY-BTZPDEILSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.94
• 重原子数：
  28.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.96
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (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 在 pyrrolidone*HBr*Br₂ 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以73%的产率得到(5aR,6S,7R,8aS,8bR,2'S,3a'R,6a'S)-8b-(hydroxymethyl)decahydro-6-(hexahydrofuro[2,3-b]furan-2'-yl)-6,7-dimethylnaphtho[1,8-bc]furan-2-ol
  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：

  (+/-)-cis,trans-(2-methoxytetrahydrofuran-3-yl)methanol 在 palladium on activated charcoal 吡啶 、 咪唑 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 copper(I) bromide dimethylsulfide complex 、 trityl perchlorate 、 水 、 氢气 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 臭氧 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 六甲基磷酰三胺 、 乙醚 、 二氯甲烷 、 氯仿 、 N,N-二甲基甲酰胺 、 甲苯 、 正戊烷 、 苯 为溶剂， 反应 159.25h， 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