(4E,8E,12E)-4,8,12-trimethyl-14-(3,4,5,6-tetrahydro-2H-pyran-2-yloxy)tetradeca-4,8,12-trienal | 152717-47-0

• 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: (4E,8E,12E)-4,8,12-trimethyl-14-(3,4,5,6-tetrahydro-2H-pyran-2-yloxy)tetradeca-4,8,12-trienal
• 英文别名: (4E,8E,12E)-4,8,12-trimethyl-14-(oxan-2-yloxy)tetradeca-4,8,12-trienal
• CAS: 152717-47-0
• 化学式: C₂₂H₃₆O₃
• 分子量: 348.526
• InChiKey: KSPKXWUFHHBOJL-RBDYADCBSA-N

物化性质

• 沸点：
  469.1±45.0 °C(Predicted)
• 密度：
  0.96±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  25
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4E,8E,12E)-4,8,12-trimethyl-14-(3,4,5,6-tetrahydro-2H-pyran-2-yloxy)tetradeca-4,8,12-trienal 在 sodium tetrahydroborate 、 三乙胺 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 36.0h， 生成 (E,E,E)-5,9,13-trimethyl-15-[(tetrahydro-2H-pyran-2-yl)oxy]pentadeca-5,9,13-trienenitrile
  参考文献：
  名称：

  Novel Regio- and Stereoselective Cascade 6-endo-trig Cyclisations from Polyene Acyl Radical Intermediates Leading to Steroid-Like Pentacycles and Heptacycles

  摘要：

  In a quite remarkable regio- and stereoselective manner, each of the (all-E)-polyene selenoates 5a-c is shown to undergo cascade radical-mediated polycyclisations via consecutive 6-endo-trig reactions, leading to the corresponding all-trans, anti, tri-, penta- and heptacycles, i.e., 20, 23, and 25, in good yields. The configurations of these 'steroid-like' polycycles followed from detailed examination and correlation of chemical shift data in their C-13-NMR spectra.

  DOI：

  10.1002/1522-2675(20000906)83:9<2629::aid-hlca2629>3.0.co;2-w
• 作为产物：
  描述：

  (E)-6-acetoxy-4-methyl-4-hexenal 在 W-2 Raney nickel 咪唑 、 2,4,6-三甲基吡啶 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 乙醇 、 Swern ox 、 四丁基氟化铵 、 甲基磺酰氯 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 乙醚 、 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.67h， 生成 (4E,8E,12E)-4,8,12-trimethyl-14-(3,4,5,6-tetrahydro-2H-pyran-2-yloxy)tetradeca-4,8,12-trienal
  参考文献：
  名称：

  Nishitani, Kiyoshi; Konomi, Toshihiko; Mimaki, Youji, Heterocycles, 1993, vol. 36, # 9, p. 1957 - 1960

  摘要：

  DOI：

文献信息

• A Biomimetic Synthesis of Sacculatane Diterpenoids
  作者：Marina Grinco、Veaceslav Kulciţki、Nicon Ungur、Pavel F. Vlad、Margherita Gavagnin、Francesco Castelluccio、Guido Cimino

  DOI：10.1002/hlca.200890031

  日期：2008.2

  The biomimetic synthesis of sacculatane-type epimeric compounds 14a and 14b is reported. The key synthetic step is the low-temperature superacidic cyclization of (all-E)-ω-acetoxygeranylgeraniol 12 obtained in nine steps from geranyllinalool (13). The 19-acetoxysacculata-7,17-dien-11-ol (14a) could be an important and convenient starting compound for the synthesis of other sacculatane diterpenoids.

  已报道了acc草型的差向异构化合物14a和14b的仿生合成。关键的合成步骤是在九个步骤中从香叶薄荷醇（13）获得的（全-E）-ω-乙酰氧基香叶基香叶醇12的低温超酸性环化。19-乙酰氧基acculata-7,17-dien-11-ol（14a）可能是合成其他sacculatane二萜类化合物的重要且方便的起始化合物。
• Importance of the isopropylidene terminal of geranylgeranyl group for the formation of tetraether lipid in methanogenic archaea
  作者：Tadashi Eguchi、Yuji Nishimura、Katsumi Kakinuma

  DOI：10.1016/s0040-4039(03)00627-0

  日期：2003.4

  Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the C-C bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this C-C bond formation. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Nishitani, Kiyoshi; Konomi, Toshihiko; Mimaki, Youji, Heterocycles, 1993, vol. 36, # 9, p. 1957 - 1960
  作者：Nishitani, Kiyoshi、Konomi, Toshihiko、Mimaki, Youji、Tsunoda, Takashi、Yamakawa, Koji

  DOI：——

  日期：——
• Novel Regio- and Stereoselective Cascade 6-endo-trig Cyclisations from Polyene Acyl Radical Intermediates Leading to Steroid-Like Pentacycles and Heptacycles
  作者：Sandeep Handa、Prathap S. Nair、Gerald Pattenden

  DOI：10.1002/1522-2675(20000906)83:9<2629::aid-hlca2629>3.0.co;2-w

  日期：2000.9.6

  In a quite remarkable regio- and stereoselective manner, each of the (all-E)-polyene selenoates 5a-c is shown to undergo cascade radical-mediated polycyclisations via consecutive 6-endo-trig reactions, leading to the corresponding all-trans, anti, tri-, penta- and heptacycles, i.e., 20, 23, and 25, in good yields. The configurations of these 'steroid-like' polycycles followed from detailed examination and correlation of chemical shift data in their C-13-NMR spectra.