(Z)-oleic pivalic anhydride | 256341-05-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Z)-oleic pivalic anhydride
• CAS: 256341-05-6
• 化学式: C₂₃H₄₂O₃
• 分子量: 366.585
• InChiKey: FYVFPFBBQIWPBY-SEYXRHQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.14
• 重原子数：
  26.0
• 可旋转键数：
  15.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (Z)-oleic pivalic anhydride 在 正丁基锂 、 sodium hexamethyldisilazane 、 magnesium methanolate 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.61h， 生成 methyl (S)-2-hydroxyoleate
  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：

  油酸 、 三甲基乙酰氯 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 生成 (Z)-oleic pivalic anhydride
  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

• Practical Access to Amines by Platinum-Catalyzed Reduction of Carboxamides with Hydrosilanes: Synergy of Dual Si−H Groups Leads to High Efficiency and Selectivity
  作者：Shiori Hanada、Emi Tsutsumi、Yukihiro Motoyama、Hideo Nagashima

  DOI：10.1021/ja9055307

  日期：2009.10.21

  The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions The rate of the reaction is dependent on the distance of two Si-H groups, 1,1,3,3-tetramethyidisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO2, CO2R, CN, C=C, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
• A versatile synthesis of tetraester polyamine lipids for gene transfection
  作者：Mike E. Lizarzaburu、Mark J. Kurth、Michael H. Nantz

  DOI：10.1016/s0040-4039(99)01934-6

  日期：1999.12

  The preparation of polyamine lipids via Michael addition of diamines to tetraester bisacrylates is described. A new pentaerythritol protection strategy enabled the synthesis of a bis(p-methoxybenzyl)diether diol which was used to prepare the saturated and unsaturated diester cores. (C) 1999 Elsevier Science Ltd. All rights reserved.