Ethyl (2Z,4E,8E,12E)-14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate | 123979-88-4

• 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: Ethyl (2Z,4E,8E,12E)-14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate
• 英文别名: ethyl (2Z,4E,8E,12E)-14-hydroxy-5,9,13-trimethyl-2-propan-2-yltetradeca-2,4,8,12-tetraenoate
• CAS: 123979-88-4
• 化学式: C₂₂H₃₆O₃
• 分子量: 348.526
• InChiKey: UNXHWEUYBZTHAP-BFMXEOMMSA-N

物化性质

• 沸点：
  466.7±33.0 °C(Predicted)
• 密度：
  0.950±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  25
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Ethyl (2Z,4E,8E,12E)-14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate 在 potassium cyanide 、 18-冠醚-6 barium permanganate 、 二异丁基氢化铝 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 10.83h， 生成 (2Z,4E,8E,12E)-2-(1-Methylethyl)-5,9,13-trimethyl-1-<(trimethylsilyl)oxy>-2,4,8,12-cyclotetradecatetraene-1-carbonitrile
  参考文献：
  名称：

  Total Synthesis of Sarcophytol A, an Anticarcinogenic Marine Cembranoid

  摘要：

  A highly stereo- and enantioselective total synthesis of sarcophytol A (1), a marine cembranoid promising as a cancer chemopreventive agent, is described. The nitrile 10 obtained Z-selectively (Z:E = >35:1) by the Horner-Emmons reaction of (E,E)-farnesal (5) with the phosphononitrile 9 in 91% yield was converted to the conjugated 2(Z),4(E)-dienal 3 in which the terminal (E)-methyl group was functionalized. Intramolecular alkylation of the cyanohydrin TMS ether of 3 provided the macrocyclic ketone 2 in 79% of overall yield from 3 without isolation of the cyclic cyanohydrin 20 as well as its TMS ether 19. Reduction of 2 with several chiral LiAlH4 reagents afforded 1 highly enantioselectively (87-93% ee) in 78-97% yield, from which enantiomerically pure 1 (>99% ee) was readily obtained upon a single recrystallization.

  DOI：

  10.1021/jo00089a011
• 作为产物：
  描述：

  2-(二乙氧基次膦酰基)-3-甲基丁酸乙酯 在 叔丁基过氧化氢 、 正丁基锂 、 selenium(IV) oxide 作用下， 以 二氯甲烷 为溶剂， 生成 Ethyl (2Z,4E,8E,12E)-14-hydroxy-2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenoate
  参考文献：
  名称：

  石蜡酚B的合成和立体化学：一种抗癌的类。

  摘要：

  据报道，使用低温，钛诱导的1,14-二醛5频哪醇偶联反应作为关键步骤，可以从法呢醛中进行短（5步）有效合成sarcophytol B（1）。X射线结构测定表明，肌醇B具有反式二醇立体化学。

  DOI：

  10.1016/s0040-4039(00)72708-0

文献信息

• Synthesis and stereochemistry of sarcophytol B: An anticancer cembranoid
  作者：John E. McMurry、Joseph G. Rico、You-nan Shih

  DOI：10.1016/s0040-4039(00)72708-0

  日期：1989.1

  A short (5 step), efficient synthesis of sarcophytol B (1) from farnesal is reported using a low-temperature, titanium-induced pinacol coupling reaction of 1,14-dialdehyde5 as the key step. An X-ray structure determination showed that sarcophytol B has trans diol stereochemistry.

  据报道，使用低温，钛诱导的1,14-二醛5频哪醇偶联反应作为关键步骤，可以从法呢醛中进行短（5步）有效合成sarcophytol B（1）。X射线结构测定表明，肌醇B具有反式二醇立体化学。
• Total Synthesis of Sarcophytol A, an Anticarcinogenic Marine Cembranoid
  作者：Hisao Takayanagi、Yasunori Kitano、Yasuhiro Morinaka

  DOI：10.1021/jo00089a011

  日期：1994.5

  A highly stereo- and enantioselective total synthesis of sarcophytol A (1), a marine cembranoid promising as a cancer chemopreventive agent, is described. The nitrile 10 obtained Z-selectively (Z:E = >35:1) by the Horner-Emmons reaction of (E,E)-farnesal (5) with the phosphononitrile 9 in 91% yield was converted to the conjugated 2(Z),4(E)-dienal 3 in which the terminal (E)-methyl group was functionalized. Intramolecular alkylation of the cyanohydrin TMS ether of 3 provided the macrocyclic ketone 2 in 79% of overall yield from 3 without isolation of the cyclic cyanohydrin 20 as well as its TMS ether 19. Reduction of 2 with several chiral LiAlH4 reagents afforded 1 highly enantioselectively (87-93% ee) in 78-97% yield, from which enantiomerically pure 1 (>99% ee) was readily obtained upon a single recrystallization.