(2S,5S,6S)-2-(1-hydroxybut-3-enyl)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane | 951388-69-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,5S,6S)-2-(1-hydroxybut-3-enyl)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane
• CAS: 951388-69-5
• 化学式: C₁₂H₂₂O₅
• 分子量: 246.304
• InChiKey: GNNYDMLSWKKZQR-LLTYBXMGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.06
• 重原子数：
  17.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (2S,5S,6S)-2-(1-hydroxybut-3-enyl)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane 在 2,2,6,6-四甲基哌啶 、 咪唑 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 5-苯基四氮唑 、 四丁基氟化铵 、 sodium hydride 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 癸烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 76.34h， 生成 (2'S,3'R,4S)-2,2-dimethyl[1,3]dioxolan-4-ylmethyl 2'-octadecanoyloxy-3'-hexadecyloxyhex-5'-enyl methyl phosphate
  参考文献：
  名称：

  Synthesis of sn-1 functionalized phospholipids as substrates for secretory phospholipase A2

  摘要：

  Secretory phospholipase A2 (sPLA2) represents a family of small water-soluble enzymes that catalyze the hydrolysis of phospholipids in the sn-2 position liberating free fatty acids and lysophospholipids. Herein we report the synthesis of two new phospholipids (1 and 2) with bulky allyl-substituents attached to the sn-1 position of the glycerol backbone. The synthesis of phospholipids 1 and 2 is based upon the construction of a key aldehyde intermediate 3 which locks the stereochemistry in the sn-2 position of the final phospholipids. The aldehyde functionality serves as the site for insertion of the allyl-substituents by a zinc mediated allylation. Small unilamellar liposomes composed of phospholipids 1 and 2 were subjected to sPLA2 activity measurements. Our results show that only phospholipid 1 is hydrolyzed by the enzyme. Molecular dynamics simulations revealed that the lack of hydrolysis of phospholipid 2 is due to steric hindrance caused by the bulky side chain of the substrate allowing only limited access of water molecules to the active site.

  DOI：

  10.1016/j.chemphyslip.2006.12.006
• 作为产物：
  描述：

  methyl (2R)-2-[(2S,5S,6S)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxan-2-yl]-2-hydroxyacetate 在 sodium tetrahydroborate 、 sodium periodate 、 碳酸氢钠 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 异丙醇 为溶剂， 反应 0.67h， 生成 (2S,5S,6S)-2-(1-hydroxybut-3-enyl)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane
  参考文献：
  名称：

  Synthesis of sn-1 functionalized phospholipids as substrates for secretory phospholipase A2

  摘要：

  Secretory phospholipase A2 (sPLA2) represents a family of small water-soluble enzymes that catalyze the hydrolysis of phospholipids in the sn-2 position liberating free fatty acids and lysophospholipids. Herein we report the synthesis of two new phospholipids (1 and 2) with bulky allyl-substituents attached to the sn-1 position of the glycerol backbone. The synthesis of phospholipids 1 and 2 is based upon the construction of a key aldehyde intermediate 3 which locks the stereochemistry in the sn-2 position of the final phospholipids. The aldehyde functionality serves as the site for insertion of the allyl-substituents by a zinc mediated allylation. Small unilamellar liposomes composed of phospholipids 1 and 2 were subjected to sPLA2 activity measurements. Our results show that only phospholipid 1 is hydrolyzed by the enzyme. Molecular dynamics simulations revealed that the lack of hydrolysis of phospholipid 2 is due to steric hindrance caused by the bulky side chain of the substrate allowing only limited access of water molecules to the active site.

  DOI：

  10.1016/j.chemphyslip.2006.12.006