(1E,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienecarbaldehyde | 196401-76-0

• 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: (1E,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienecarbaldehyde
• 英文别名: (1E,7E)-7-methyl-4-propan-2-ylidenecyclodeca-1,7-diene-1-carbaldehyde
• CAS: 196401-76-0
• 化学式: C₁₅H₂₂O
• 分子量: 218.339
• InChiKey: BTVJNLGZZNFMLL-MXENDMJBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1E,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienecarbaldehyde 在 正丁基锂 、 四甲基乙二胺 、 TMPDCl 、 lithium 、 乙胺 、 红铝 作用下， 以 甲苯 为溶剂， 反应 1.92h， 生成 (E,E)-germacra-1(10),4,7(11)-triene
  参考文献：
  名称：

  Synthesis of (E,E)-Germacrane Sesquiterpene Alcohols via Enolate-Assisted 1,4-Fragmentation

  摘要：

  An efficient method has been developed for the synthesis of (E,E)-germacrane sesquiterpene alcohols, The key step in these syntheses involves the enolate-assisted 1,4-fragmentation of properly functionalized perhydro-1-naphthalenecarboxaldehydes with 1 equiv of sodium tert-amylate as base, to give the corresponding (E,E)-germacrane aldehydes. These aldehydes are not very stable, and in situ reduction of the aldehyde function with Red-Al is required to obtain high yields of the desired germacrane alcohols. This procedure has led to the successful synthesis of 15-hydroxygermacrene B (4) and 15-hydroxyhedycaryol (35) from the mesylates 6 and 33, respectively. When KHMDS is used instead of sodium tert-amylate in the fragmentation reaction of 6, isomerization of the initially formed C(4)-C(5) E double bond cannot be avoided and results, after in situ reduction with Red-Al, in the formation of the (E,Z)-germacrane alcohol 24. The 15-hydroxg-(E,E)-germacranes are excellent starting materials for the selective synthesis of the corresponding 4,5-epoxides, which in turn can perfectly well be used in studies on the biomimetic formation of guaiane sesquiterpenes.

  DOI：

  10.1021/jo970901z
• 作为产物：
  描述：

  Methanesulfonic acid (1S,4R,4aR,8aS)-4-formyl-6-isopropylidene-8a-methyl-decahydro-naphthalen-1-yl ester 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 以27%的产率得到(1E,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienecarbaldehyde
  参考文献：
  名称：

  Synthesis of (E,E)-Germacrane Sesquiterpene Alcohols via Enolate-Assisted 1,4-Fragmentation

  摘要：

  An efficient method has been developed for the synthesis of (E,E)-germacrane sesquiterpene alcohols, The key step in these syntheses involves the enolate-assisted 1,4-fragmentation of properly functionalized perhydro-1-naphthalenecarboxaldehydes with 1 equiv of sodium tert-amylate as base, to give the corresponding (E,E)-germacrane aldehydes. These aldehydes are not very stable, and in situ reduction of the aldehyde function with Red-Al is required to obtain high yields of the desired germacrane alcohols. This procedure has led to the successful synthesis of 15-hydroxygermacrene B (4) and 15-hydroxyhedycaryol (35) from the mesylates 6 and 33, respectively. When KHMDS is used instead of sodium tert-amylate in the fragmentation reaction of 6, isomerization of the initially formed C(4)-C(5) E double bond cannot be avoided and results, after in situ reduction with Red-Al, in the formation of the (E,Z)-germacrane alcohol 24. The 15-hydroxg-(E,E)-germacranes are excellent starting materials for the selective synthesis of the corresponding 4,5-epoxides, which in turn can perfectly well be used in studies on the biomimetic formation of guaiane sesquiterpenes.

  DOI：

  10.1021/jo970901z

文献信息

• Synthesis of (<i>E</i>,<i>E</i>)-Germacrane Sesquiterpene Alcohols via Enolate-Assisted 1,4-Fragmentation
  作者：Adriaan J. Minnaard、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo970901z

  日期：1997.10.1

  An efficient method has been developed for the synthesis of (E,E)-germacrane sesquiterpene alcohols, The key step in these syntheses involves the enolate-assisted 1,4-fragmentation of properly functionalized perhydro-1-naphthalenecarboxaldehydes with 1 equiv of sodium tert-amylate as base, to give the corresponding (E,E)-germacrane aldehydes. These aldehydes are not very stable, and in situ reduction of the aldehyde function with Red-Al is required to obtain high yields of the desired germacrane alcohols. This procedure has led to the successful synthesis of 15-hydroxygermacrene B (4) and 15-hydroxyhedycaryol (35) from the mesylates 6 and 33, respectively. When KHMDS is used instead of sodium tert-amylate in the fragmentation reaction of 6, isomerization of the initially formed C(4)-C(5) E double bond cannot be avoided and results, after in situ reduction with Red-Al, in the formation of the (E,Z)-germacrane alcohol 24. The 15-hydroxg-(E,E)-germacranes are excellent starting materials for the selective synthesis of the corresponding 4,5-epoxides, which in turn can perfectly well be used in studies on the biomimetic formation of guaiane sesquiterpenes.