((1Z,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienyl)-methanol | 195870-66-7

• 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: ((1Z,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienyl)-methanol
• 英文别名: [(1Z,7E)-7-methyl-4-propan-2-ylidenecyclodeca-1,7-dien-1-yl]methanol
• CAS: 195870-66-7
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: VXDLKRURXJIDCG-DZEVCYDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ((1Z,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienyl)-methanol 在 正丁基锂 、 四甲基乙二胺 、 TMPDCl 、 lithium 、 乙胺 作用下， 生成 (1E,5E)-1,5-二甲基-8-(丙-2-亚基)环癸-1,5-二烯
  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：

  (1Z,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienecarbaldehyde 在 红铝 作用下， 以 甲苯 为溶剂， 反应 0.25h， 生成 ((1Z,7E)-4-Isopropylidene-7-methyl-cyclodeca-1,7-dienyl)-methanol
  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

• About the Chiral Stability of Germacrene B and the Biomimetic Synthesis of Guaiane Sesquiterpenes
  作者：Adriaan J. Minnaard、Joannes B. P. A. Wijnberg、Aede de Groot

  DOI：10.1021/jo970902r

  日期：1997.10.1

  of the optically active cis-fused guaiane 4 of high ee with limited Sharpless reagent shows that the asymmetric epoxidation of 2 proceeds highly enantioselectively. The Sharpless epoxidation methodology applied on the (E,Z)-germacrane 3 results in the formation of the stable optically active epoxide 5. Acid-induced cyclization of 5, leading to a mixture of guaianes, probably proceeds via the trans-fused

  15-羟基germacrene B（2）的平面手性已通过不对称的Sharpless环氧化法进行了检查，以动力学拆分的方式进行。用Eu（hfc）（3）进行的（1）H NMR实验表明，回收的2是外消旋的。因此，2和最有可能的胚germ B（1）在室温下对映体不稳定。高ee的光学活性顺式融合的愈创木酚4和少量Sharpless试剂的形成表明2的不对称环氧化高度对映选择性地进行。在（E，Z）-germacrane 3上使用的Sharpless环氧化方法可形成稳定的旋光环氧化合物5。酸诱导的5的环化反应，生成愈创树酯的混合物，可能是通过反熔碳正离子中间体进行的一种。