(E)-(S)-3,7,11-Trimethyl-dodeca-2,10-dienal | 127231-65-6

• 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: (E)-(S)-3,7,11-Trimethyl-dodeca-2,10-dienal
• CAS: 127231-65-6
• 化学式: C₁₅H₂₆O
• 分子量: 222.371
• InChiKey: PGOZFBLSBPFUDH-XDPMZMSMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.68
• 重原子数：
  16.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (E)-(S)-3,7,11-Trimethyl-dodeca-2,10-dienal 在 <3H>NaBH4 作用下， 以 异丙醇 为溶剂， 生成 <1-3H>-(7S)-trans-6,7-dihydrofarnesol
  参考文献：
  名称：

  Trichodiene Synthase. Stereochemical Studies of the Cryptic Allylic Diphosphate Isomerase Activity Using an Anomalous Substrate

  摘要：

  Incubation of (7S)-6,7-dihydrofarnesyl diphosphate with trichodiene synthase gave, as previously described, a mixture consisting of 80% dihydrofarnesene isomers 6-8 accompanied by 6% trans- 6,7-dihydrofarnesol (10) and 13% 6,7-dihydronerolidol (9). The latter product has now been shown to be (3S,7S)-6,7-dihydronerolidol [(3S,7S)-9] by direct comparison with synthetic (3S,7S)-6,7-dihydronerolidol and (3RS,7S)-6,7-dihydronerolidol using chiral capillary gas chromatography. The observed formation of (3S,7S)-9 can be accounted for by backside attack of water on an allylic cation-pyrophosphate anion pair generated by syn allylic rearrangement of dihydrofarnesyl diphosphate (5) and ionization of the resulting (3R,7S)-6,7-dihydronerolidyl diphosphate (14). These results provide further support for the proposed isomerization of farnesyl diphosphate (1) to (3R)-nerolidyl diphosphate (3) in the enzymatic formation trichodiene (2).

  DOI：

  10.1021/jo00098a046
• 作为产物：
  描述：

  (7S)-trans-6,7-dihydrofarnesyl diphosphate 在 manganese(IV) oxide 、 ammonium hydroxide 、 Buffer H (pH: 7.2) 作用下， 以 正己烷 为溶剂， 反应 1.17h， 生成 (E)-(S)-3,7,11-Trimethyl-dodeca-2,10-dienal
  参考文献：
  名称：

  Trichodiene Synthase. Stereochemical Studies of the Cryptic Allylic Diphosphate Isomerase Activity Using an Anomalous Substrate

  摘要：

  Incubation of (7S)-6,7-dihydrofarnesyl diphosphate with trichodiene synthase gave, as previously described, a mixture consisting of 80% dihydrofarnesene isomers 6-8 accompanied by 6% trans- 6,7-dihydrofarnesol (10) and 13% 6,7-dihydronerolidol (9). The latter product has now been shown to be (3S,7S)-6,7-dihydronerolidol [(3S,7S)-9] by direct comparison with synthetic (3S,7S)-6,7-dihydronerolidol and (3RS,7S)-6,7-dihydronerolidol using chiral capillary gas chromatography. The observed formation of (3S,7S)-9 can be accounted for by backside attack of water on an allylic cation-pyrophosphate anion pair generated by syn allylic rearrangement of dihydrofarnesyl diphosphate (5) and ionization of the resulting (3R,7S)-6,7-dihydronerolidyl diphosphate (14). These results provide further support for the proposed isomerization of farnesyl diphosphate (1) to (3R)-nerolidyl diphosphate (3) in the enzymatic formation trichodiene (2).

  DOI：

  10.1021/jo00098a046