(9Z,11E)-13-(2-methoxypropan-2-ylperoxy)octadeca-9,11-dienoic acid | 1221277-95-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (9Z,11E)-13-(2-methoxypropan-2-ylperoxy)octadeca-9,11-dienoic acid
• CAS: 1221277-95-7
• 化学式: C₂₂H₄₀O₅
• 分子量: 384.557
• InChiKey: PCJVQNGCMBWSMX-HCMZBRDFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.19
• 重原子数：
  27.0
• 可旋转键数：
  18.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  64.99
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (9Z,11E)-13-(2-methoxypropan-2-ylperoxy)octadeca-9,11-dienoic acid 在 氧气 、 4-甲基苯磺酸吡啶 、 tetraphenylporphyrin 、 天然维生素E 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 98.0h， 生成 (E)-9-hydroxy-12-oxo-10-dodecenoic acid
  参考文献：
  名称：

  An ¹O₂ Route to γ-Hydroxyalkenal Phospholipids by Vitamin E-Induced Fragmentation of Hydroperoxydiene-Derived Endoperoxides

  摘要：

  Biologically active phospholipids that incorporate an oxidatively truncated acyl chain terminated by a gamma-hydroxyalkenal are generated in vivo. The gamma-hydroxyalkenal moiety protrudes from lipid bilayers like whiskers that serve as ligands for the scavenger receptor CD36, fostering endocytosis, e.g., of oxidatively damaged photoreceptor cell outer segments by retinal pigmented endothelial cells. They also covalently modify proteins generating carboxyalkyl pyrroles incorporating the E-amino group of protein lysyl residues. We postulated that gamma-hydroxyalkenals could be generated, e.g., in the eye, through fragmentation of hydroperoxy endoperoxides produced in the retina through reactions of singlet molecular oxygen with polyunsaturated phospholipids. Since phospholipid esters are far more abundant in the retina than free fatty acids, we examined the influence of a membrane environment on the fate of hydroperoxy endoperoxides. We now report that linoleate hydroperoxy endoperoxides in thin films and their phospholipid esters in biomimetic membranes fragment to gamma-hydroxyalkenals, and fragmentation is stoichiometrically induced by vitamin E. The product distribution from fragmentation of the free acid in the homogeneous environment of a thin film is remarkably different from that from the corresponding phospholipid in a membrane. In the membrane, further oxidation of the initially formed gamma-hydroxyalkenal to a butenolide is disfavored. A conformational preference for the gamma-hydroxyalkenal, to protrude from the membrane into the aqueous phase, may protect it from oxidation induced by lipid hydroperoxides that remain buried in the lipophilic membrane core.

  DOI：

  10.1021/tx200093m
• 作为产物：
  描述：

  2-甲氧基丙烯 、 (9Z,11E)-13-hydroperoxyoctadeca-9,11-dienoic acid 在 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以78%的产率得到(9Z,11E)-13-(2-methoxypropan-2-ylperoxy)octadeca-9,11-dienoic acid
  参考文献：
  名称：

  An ¹O₂ Route to γ-Hydroxyalkenal Phospholipids by Vitamin E-Induced Fragmentation of Hydroperoxydiene-Derived Endoperoxides

  摘要：

  Biologically active phospholipids that incorporate an oxidatively truncated acyl chain terminated by a gamma-hydroxyalkenal are generated in vivo. The gamma-hydroxyalkenal moiety protrudes from lipid bilayers like whiskers that serve as ligands for the scavenger receptor CD36, fostering endocytosis, e.g., of oxidatively damaged photoreceptor cell outer segments by retinal pigmented endothelial cells. They also covalently modify proteins generating carboxyalkyl pyrroles incorporating the E-amino group of protein lysyl residues. We postulated that gamma-hydroxyalkenals could be generated, e.g., in the eye, through fragmentation of hydroperoxy endoperoxides produced in the retina through reactions of singlet molecular oxygen with polyunsaturated phospholipids. Since phospholipid esters are far more abundant in the retina than free fatty acids, we examined the influence of a membrane environment on the fate of hydroperoxy endoperoxides. We now report that linoleate hydroperoxy endoperoxides in thin films and their phospholipid esters in biomimetic membranes fragment to gamma-hydroxyalkenals, and fragmentation is stoichiometrically induced by vitamin E. The product distribution from fragmentation of the free acid in the homogeneous environment of a thin film is remarkably different from that from the corresponding phospholipid in a membrane. In the membrane, further oxidation of the initially formed gamma-hydroxyalkenal to a butenolide is disfavored. A conformational preference for the gamma-hydroxyalkenal, to protrude from the membrane into the aqueous phase, may protect it from oxidation induced by lipid hydroperoxides that remain buried in the lipophilic membrane core.

  DOI：

  10.1021/tx200093m