8-(5-oxo-2,5-dihydrofuran-2-yl)-octanoic acid

• 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: 8-(5-oxo-2,5-dihydrofuran-2-yl)-octanoic acid
• 英文别名: 8-(5-Oxo-2,5-dihydrofuran-2-yl) octanoic acid；8-(5-oxo-2H-furan-2-yl)octanoic acid
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: BPQSIKKFAFZGEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  8-(5-oxo-2,5-dihydrofuran-2-yl)-octanoic acid 、 α-溴-2,3,4,5,6-五氟甲基苯酸酯 在 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 perfluorobenzyl 8-(5-oxo-2,5-dihydrofuran-2-yl)octanoate
  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：

  8-(2-Furyl)octansaeure 在 sodium chlorite 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 作用下， 以 甲醇 、 水 、 叔丁醇 为溶剂， 反应 2.0h， 生成 8-(5-oxo-2,5-dihydrofuran-2-yl)-octanoic 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

文献信息

• Characterization of Bitter-Tasting Oxylipins in Poppy Seeds (<i>Papaver somniferum</i> L.)
  作者：Johanna Lainer、Corinna Dawid、Andreas Dunkel、Peter Gläser、Stephanie Wittl、Thomas Hofmann

  DOI：10.1021/acs.jafc.9b06655

  日期：2020.9.23

  time-of-flight mass spectrometry, tandem mass spectrometry, and one-/two-dimensional nuclear magnetic resonance experiments, revealed the chemical structures of five bitter-tasting fatty acids (1–5), three monoglycerides (6–8), six C18-lipidoxidation products (9–14), and four lipid oxidation degradation products (15 and 17–19) as well as two previously unreported monoglyceride oxidation degradation

  罂粟籽（的活性引导分馏罂粟L.）提取物和脂肪酸氧化模型实验分析，然后通过液相色谱时间飞行质谱，串联质谱，和单/二维核磁共振实验透出五个苦味脂肪酸（化学结构15），三甘油单酯（6 - 8），6个C 18个-lipidoxidation产品（9 - 14），和四个脂质氧化降解产物（15和17 - 19）以及两个以前未报告的甘油单酸酯氧化降解产物，即9-（2'，3'-二羟丙氧基）-9-氧羰酸（1-azeloyl- rac -glycerol ，16）和1-（2'，3' -二羟丙基）-8-（5″-氧代-2″，5″-二氢fruan-2″-基）-辛酸酯（1-ODFO- rac-甘油，20）。感官研究显示苦味阈值浓度在0.08至0.29 mmol / L之间，特别是对于较高氧化度的C 18-脂肪酸三羟基十八烯酸（THOE，12），12,13-二羟基-9-氧代-10-辛烯酸（12 ，13-diOH-9-oxo，13）和9
• Fe²⁺ Catalyzes Vitamin E-Induced Fragmentation of Hydroperoxy and Hydroxy Endoperoxides That Generates γ-Hydroxy Alkenals
  作者：Xiaodong Gu、Wujuan Zhang、Robert G. Salomon

  DOI：10.1021/ja0689785

  日期：2007.5.1

  The formation of cytotoxic gamma-hydroxyalkenals has been generally viewed as the consequence of free radical-induced oxidation of polyunsaturated fatty acyls through the decomposition of lipid peroxides. Vitamin E (Vit E) would be expected to inhibit such autoxidation. In a model study, we now find that fragmentation of a hydroperoxy endoperoxide generated the lactone of a gamma-hydroxyalkenal. With 1 equiv of Fe2+, or with a catalytic amount (0.1 equiv) of Fe2+ and 1 equiv of Vit E, the yields are 43-50%. However, Vit E alone did not promote the fragmentation, and a catalytic amount of Fe2+ alone only afforded a low yield (about 5%). Vit E could contribute to, as opposed to preventing, the formation of gamma-hydroxyalkenals by converting redox-active metal ions into their reduced forms that promote the rapid fragmentation of hydroperoxy endoperoxides.
• An ¹O₂ Route to γ-Hydroxyalkenal Phospholipids by Vitamin E-Induced Fragmentation of Hydroperoxydiene-Derived Endoperoxides
  作者：Xiaodong Gu、Wujuan Zhang、Jaewoo Choi、Wei Li、Xi Chen、James M. Laird、Robert G. Salomon

  DOI：10.1021/tx200093m

  日期：2011.7.18

  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.