(2S,5S,6S)-2-(5,6-dimethoxy-5,6-dimethyl-1,4-dioxacyclohexane)carboxyaldehyde | 503320-98-7

• 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-(5,6-dimethoxy-5,6-dimethyl-1,4-dioxacyclohexane)carboxyaldehyde
• 英文别名: (2S,5S,6S)-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2-carbaldehyde；(2S,5S,6S)-5,6-dimethoxy-5,6-dimethyl[1,4]dioxane-2-carbaldehyde
• CAS: 503320-98-7
• 化学式: C₉H₁₆O₅
• 分子量: 204.223
• InChiKey: YXSZYYZZBLCEHB-VGMNWLOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2S,5S,6S)-2-(5,6-dimethoxy-5,6-dimethyl-1,4-dioxacyclohexane)carboxyaldehyde 在 1,8-双二甲氨基萘 、 氯化铵 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 144.17h， 生成 (1'R,2S,5S,6S)-2-[1'-(hexadecyloxy)-2',2'-dimethylbut-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
• 作为产物：
  描述：

  (R)-5-((2S,5S,6S)-5,6-Dimethoxy-5,6-dimethyl-[1,4]dioxan-2-yl)-3,4-dihydroxy-5H-furan-2-one 在 sodium tetrahydroborate 、 sodium periodate 、 双氧水 、 碳酸氢钠 、 potassium carbonate 作用下， 以 二氯甲烷 、 异丙醇 、 丙酮 为溶剂， 反应 4.0h， 生成 (2S,5S,6S)-2-(5,6-dimethoxy-5,6-dimethyl-1,4-dioxacyclohexane)carboxyaldehyde
  参考文献：
  名称：

  丁烷-1,2-二缩醛保护的甘油醛和(R,R)-丁烷-1,2-二缩醛-保护的乙醇酸的对映异构体的合成

  摘要：

  分别由 D-甘露醇和 L-抗坏血酸完成了方便且可扩展的丁烷-2,3-二缩醛保护的甘油醛对映异构体的合成。R-醛另外转化为 (R,R)-丁烷-2,3-二缩醛乙醇酸结构单元 1。

  DOI：

  10.1055/s-2003-40519

文献信息

• Synthesis of Enantiomers ofButane-1,2-diacetal-Protected Glyceraldehyde and of (<i>R</i>,<i>R</i>)-Butane-1,2-diacetal-ProtectedGlycolic Acid
  作者：Steven V. Ley、Patrick Michel

  DOI：10.1055/s-2003-40519

  日期：——

  A convenient and scalable synthesis of enantiomers of butane-2,3-diacetal-protected glyceraldehyde was accomplished from D-mannitol and L-ascorbic acid, respectively. The R-aldehyde was additionally converted to the (R,R)-butane-2,3-diacetal glycolic acid building block 1.

  分别由 D-甘露醇和 L-抗坏血酸完成了方便且可扩展的丁烷-2,3-二缩醛保护的甘油醛对映异构体的合成。R-醛另外转化为 (R,R)-丁烷-2,3-二缩醛乙醇酸结构单元 1。
• Highly stereoselective methylene transfers onto butanediacetal-protected chiral non-racemic sulfinyl imines using S-ylide technology
  作者：David C. Forbes、Sampada V. Bettigeri、Susanna C. Pischek

  DOI：10.1039/b822779a

  日期：——

  Diastereomeric ratios of >95 : 5 were obtained when performing methylene transfers onto imines originating from D-mannitol and (S)-(−)-2-methyl-2-propane sulfinamide or ascorbic acid and (R)-(−)-2-methyl-2-propane sulfinamide.

  在将亚甲基转移到来源于D-甘露醇和(S)-(−)-2-甲基-2-丙烷亚磺酰胺或抗坏血酸和(R)-(−)-2-甲基-2-丙烷亚磺酰胺的亚胺时，得到了大于95 : 5的非对映异构体比例。
• Butane-2,3-diacetals of Glyceraldehyde: A Stable Alternative to Glyceraldehyde Acetonide
  作者：Patrick Michel、Steven V. Ley

  DOI：10.1002/1521-3773(20021018)41:20<3898::aid-anie3898>3.0.co;2-b

  日期：2002.10.18
• Synthesis of sn-1 functionalized phospholipids as substrates for secretory phospholipase A2
  作者：Lars Linderoth、Günther H. Peters、Kent Jørgensen、Robert Madsen、Thomas L. Andresen

  DOI：10.1016/j.chemphyslip.2006.12.006

  日期：2007.3

  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.