(1Z,5E)-1-(ethoxycarbonyl)-6,10-dimethylundeca-1,5,9-trien-2-yl diethyl phosphate | 157327-72-5

• 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,5E)-1-(ethoxycarbonyl)-6,10-dimethylundeca-1,5,9-trien-2-yl diethyl phosphate
• 英文别名: ethyl (2Z,6E)-3-[(diethoxyphosphoryl)oxy]-7,11-dimethyl-2,6,10-dodecatrienoate
• CAS: 157327-72-5
• 化学式: C₂₀H₃₅O₆P
• 分子量: 402.468
• InChiKey: DJIFXTZCEWRQAL-RVJCWKLDSA-N

物化性质

• 沸点：
  463.7±45.0 °C(Predicted)
• 密度：
  1.043±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  27.0
• 可旋转键数：
  14.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (1Z,5E)-1-(ethoxycarbonyl)-6,10-dimethylundeca-1,5,9-trien-2-yl diethyl phosphate 在 sodium hydroxide 、 copper(l) iodide 、 甲基锂 、 碳酸氢钠 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 3.0h， 生成 (E,E)-法尼酸
  参考文献：
  名称：

  1,5,9-三烯的高锰酸盐氧化：含四氢呋喃片段的立体选择性合成。

  摘要：

  法呢酸酯12a-d的高锰酸盐氧化提供了过氢-2,2'-二呋喃基化合物16a-d，并控制了四个新的立体中心的相对立体化学。随后进行16a-d的氧化裂解，得到含四氢呋喃的片段17a-d，其中一个17b具有与聚醚类抗生素塞杜霉素（1）的C13-C21部分相同的相对立体化学。绝对立体化学的控制是通过使用Oppolzer sultam手性助剂实现的。只需三步即可从香叶基氯化物或神经酰氯立体选择性地制备必要的起始三烯，从而为合成聚醚片段提供了一条短而通用的途径。

  DOI：

  10.1021/jo026295b
• 作为产物：
  描述：

  ethyl acetoacetate sodium salt 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 (1Z,5E)-1-(ethoxycarbonyl)-6,10-dimethylundeca-1,5,9-trien-2-yl diethyl phosphate
  参考文献：
  名称：

  A Pd(0)-catalyzed route to 13-methylidenefarnesyl diphosphate

  摘要：

  The synthesis of the novel FPP analog 13-methylidenefarnesyl diphosphate 2 is described. The key step in the synthetic sequence involved the stereoselective coupling of enol triflate 8 with vinyltributyltin using Pd(AsPh(3))(2) and CuI as catalysts to afford primarily the desired cis-divinylester 7. It is also demonstrated that other 3-substituted famesyl analogs can be prepared by this Pd(0)catalyzed route.

  DOI：

  10.1016/s0040-4039(00)77157-7

文献信息

• A 1,6-Ring Closure Mechanism for (+)-δ-Cadinene Synthase?
  作者：Juan A. Faraldos、David J. Miller、Verónica González、Zulfa Yoosuf-Aly、Oscar Cascón、Amang Li、Rudolf K. Allemann

  DOI：10.1021/ja211820p

  日期：2012.4.4

  Recombinant (+)-delta-cadinene synthase (DCS) from Gossypium arboreum catalyzes the metal-dependent cyclization of (E,E)-farnesyl diphosphate (FDP) to the cadinane sesquiterpene delta-cadinene, the parent hydrocarbon of cotton phytoalexins such as gossypol. In contrast to some other sesquiterpene cyclases, DCS carries out this transformation with >98% fidelity but, as a consequence, leaves no mechanistic traces of its mode of action. The formation of (+)-delta-cadinene has been shown to occur via the enzyme-bound intermediate (3R)-nerolidyl diphosphate (NDP), which in turn has been postulated to be converted to cis-germacradienyl cation after a 1,10-cyclization. A subsequent 1,3-hydride shift would then relocate the carbocation within the transient macrocycle to expedite a second cyclization that yields the cadinenyl cation with the correct cis stereochemistry found in (+)-delta-cadinene. An elegant 1,10-mechanistic pathway that avoids the formation of (3R)-NDP has also been suggested. In this alternative scenario, the final cadinenyl cation is proposed to be formed through the intermediacy of trans, trans-germacradienyl cation and germacrene D. In addition, an alternative 1,6-ring closure mechanism via the bisabolyl cation has previously been envisioned. We report here a detailed investigation of the catalytic mechanism of DCS using a variety of mechanistic probes including, among others, deuterated and fluorinated FDPs. Farnesyl diphosphate analogues with fluorine at C2 and C10 acted as inhibitors of DCS, but intriguingly, after prolonged overnight incubations, they yielded 2F-germacrene(s) and a 10F-humulene, respectively. The observed 1,10-, and to a lesser extent, 1,11-cyclization activity of DCS with these fluorinated substrates is consistent with the postulated macrocyclization mechanism(s) en route to (+)-delta-cadinene. On the other hand, mechanistic results from incubations of DCS with 6F-FPP, (2Z,6E)-FDP, neryl diphosphate, 6,7-dihydro-FDP, and NDP seem to be in better agreement with the potential involvement of the alternative biosynthetic 1,6-ring closure pathway. In particular, the strong inhibition of DCS by 6F-FDP, coupled to the exclusive bisabolyl- and terpinyl-derived product profiles observed for the DCS-catalyzed turnover of (2Z,6E)-farnesyl and neryl diphosphates, suggested the intermediacy of alpha-bisabolyl cation. DCS incubations with enantiomerically pure [1-H-2(1)](1R)-FDP revealed that the putative bisabolyl-derived 1,6-pathway proceeds through (3R)-nerolidyl diphosphate (NDP), is consistent with previous deuterium-labeling studies, and accounts for the cis stereochemistry characteristic of cadinenyl-derived sesquiterpenes. While the results reported here do not unambiguously rule in favor of 1,6- or 1,10-cyclization, they demonstrate the mechanistic versatility inherent to DCS and highlight the possible existence of multiple mechanistic pathways.