(9Z,12Z)-(R)-2-Hydroxy-octadeca-9,12-dienoic acid methyl ester | 339170-38-6

• 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,12Z)-(R)-2-Hydroxy-octadeca-9,12-dienoic acid methyl ester
• 英文别名: methyl (2R,9Z,12Z)-2-hydroxyoctadeca-9,12-dienoate
• CAS: 339170-38-6
• 化学式: C₁₉H₃₄O₃
• 分子量: 310.477
• InChiKey: CIOUQKGNHMSZRR-UKZDDFKXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  22
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-(+)-α-乙酰氧基苯乙酸 、 (9Z,12Z)-(R)-2-Hydroxy-octadeca-9,12-dienoic acid methyl ester 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以98%的产率得到
  参考文献：
  名称：

  通过手性恶唑烷酮羧酰亚胺的高选择性不对称合成2-羟基脂肪酸甲酯

  摘要：

  AbstractHighly selective asymmetric synthesis of 2‐hydroxy fatty acid methyl esters has been accomplioshed through chiral imide enolates. Five chiral oleic acid imides were prepared by reaction of oleioc acid with pivaloyl chloride followed by reaction with five different lithiated chiral oxazolidinones including (R)‐(+)‐4‐benzyl‐2‐, (S)‐(‐)‐4‐benzyl‐2‐, (4R,5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐, (4S,5R)‐(‐)‐4‐methyl‐5‐phenyl‐2‐, and (R)‐(+)‐4‐isopropyl‐2‐oxazolidinones in 88–92% yileds. The chiral imides were reacted with NaN(Me3Si)2 at −78°C to give enolates, which subsequently reacted with 2‐(phenylsulfonyl)‐3‐phenyloxaziridine to give hydroxylated products in 78–83% yields. Methanolysis of the hydroxylated products with magnesium methoxide gave methyl 2‐hydroxyoleate. Enantiomeric excesses (ee) of the products were determined to be very high (98–99% ee) by 1H nuclear magnetic resonance study after esterification of the hydroxy group with (S)‐(+)‐O‐acetylmandelic acid. Enantioselective hydroxylation of other fatty acids including elaidic, petroselinic, vaccenic, and linoleic was evaluated under the similar conditions using (4R, 5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐oxazolidinone as a chiral auxiliary to give 98% ee values for all cases.

  DOI：

  10.1007/s11746-001-0244-9
• 作为产物：
  描述：

  (Z,Z)-9,12-十八烷二烯酸二聚物 在 正丁基锂 、 sodium hexamethyldisilazane 、 magnesium methanolate 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.28h， 生成 (9Z,12Z)-(R)-2-Hydroxy-octadeca-9,12-dienoic acid methyl ester
  参考文献：
  名称：

  通过手性恶唑烷酮羧酰亚胺的高选择性不对称合成2-羟基脂肪酸甲酯

  摘要：

  AbstractHighly selective asymmetric synthesis of 2‐hydroxy fatty acid methyl esters has been accomplioshed through chiral imide enolates. Five chiral oleic acid imides were prepared by reaction of oleioc acid with pivaloyl chloride followed by reaction with five different lithiated chiral oxazolidinones including (R)‐(+)‐4‐benzyl‐2‐, (S)‐(‐)‐4‐benzyl‐2‐, (4R,5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐, (4S,5R)‐(‐)‐4‐methyl‐5‐phenyl‐2‐, and (R)‐(+)‐4‐isopropyl‐2‐oxazolidinones in 88–92% yileds. The chiral imides were reacted with NaN(Me3Si)2 at −78°C to give enolates, which subsequently reacted with 2‐(phenylsulfonyl)‐3‐phenyloxaziridine to give hydroxylated products in 78–83% yields. Methanolysis of the hydroxylated products with magnesium methoxide gave methyl 2‐hydroxyoleate. Enantiomeric excesses (ee) of the products were determined to be very high (98–99% ee) by 1H nuclear magnetic resonance study after esterification of the hydroxy group with (S)‐(+)‐O‐acetylmandelic acid. Enantioselective hydroxylation of other fatty acids including elaidic, petroselinic, vaccenic, and linoleic was evaluated under the similar conditions using (4R, 5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐oxazolidinone as a chiral auxiliary to give 98% ee values for all cases.

  DOI：

  10.1007/s11746-001-0244-9

文献信息

• Highly selective asymmetric synthesis of 2-hydroxy fatty acid methyl esters through chiral oxazolidinone carboximides
  作者：Hong-Sik Hwang、Sevim Z. Erhan

  DOI：10.1007/s11746-001-0244-9

  日期：2001.2

  AbstractHighly selective asymmetric synthesis of 2‐hydroxy fatty acid methyl esters has been accomplioshed through chiral imide enolates. Five chiral oleic acid imides were prepared by reaction of oleioc acid with pivaloyl chloride followed by reaction with five different lithiated chiral oxazolidinones including (R)‐(+)‐4‐benzyl‐2‐, (S)‐(‐)‐4‐benzyl‐2‐, (4R,5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐, (4S,5R)‐(‐)‐4‐methyl‐5‐phenyl‐2‐, and (R)‐(+)‐4‐isopropyl‐2‐oxazolidinones in 88–92% yileds. The chiral imides were reacted with NaN(Me3Si)2 at −78°C to give enolates, which subsequently reacted with 2‐(phenylsulfonyl)‐3‐phenyloxaziridine to give hydroxylated products in 78–83% yields. Methanolysis of the hydroxylated products with magnesium methoxide gave methyl 2‐hydroxyoleate. Enantiomeric excesses (ee) of the products were determined to be very high (98–99% ee) by 1H nuclear magnetic resonance study after esterification of the hydroxy group with (S)‐(+)‐O‐acetylmandelic acid. Enantioselective hydroxylation of other fatty acids including elaidic, petroselinic, vaccenic, and linoleic was evaluated under the similar conditions using (4R, 5S)‐(+)‐4‐methyl‐5‐phenyl‐2‐oxazolidinone as a chiral auxiliary to give 98% ee values for all cases.