methyl (E)-14-hydroxy-12-methylidenepentadec-9-enoate | 392742-75-5

• 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: methyl (E)-14-hydroxy-12-methylidenepentadec-9-enoate
• CAS: 392742-75-5
• 化学式: C₁₇H₃₀O₃
• 分子量: 282.423
• InChiKey: QBWJFFIHPSMMKR-CSKARUKUSA-N

物化性质

• 沸点：
  381.2±37.0 °C(Predicted)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  20
• 可旋转键数：
  13
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  methyl (E)-14-hydroxy-12-methylidenepentadec-9-enoate 在 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ sodium hydroxide 、 乙氧基乙炔 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 反应 37.33h， 生成 (10E)-15-methyl-13-methylidene-1-oxacyclopentadec-10-en-2-one
  参考文献：
  名称：

  An Acid-Catalyzed Macrolactonization Protocol

  摘要：

  [GRAPHICS]An efficient macrolactonization protocol devoid of any base was developed derived from the use of vinyl esters in transesterification. Subjecting a hydroxy acid and ethoxyacetylene to 2 mol % [RuCl2(p-cymene)](2) in toluene followed by addition of camphorsulfonic acid or inverse addition provided macrolactones in good yields.

  DOI：

  10.1021/ol026726c
• 作为产物：
  描述：

  4-戊炔-2-醇 、 10-烯酸甲酯 在 cyclopentadienylruthenium(II) trisacetonitrile hexafluorophosphate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 methyl (E)-14-hydroxy-12-methylidenepentadec-9-enoate
  参考文献：
  名称：

  An Acid-Catalyzed Macrolactonization Protocol

  摘要：

  [GRAPHICS]An efficient macrolactonization protocol devoid of any base was developed derived from the use of vinyl esters in transesterification. Subjecting a hydroxy acid and ethoxyacetylene to 2 mol % [RuCl2(p-cymene)](2) in toluene followed by addition of camphorsulfonic acid or inverse addition provided macrolactones in good yields.

  DOI：

  10.1021/ol026726c

文献信息

• Synthesis of 1,1-Disubstituted Alkenes via a Ru-Catalyzed Addition
  作者：Barry M. Trost、Anthony B. Pinkerton、F. Dean Toste、Martin Sperrle

  DOI：10.1021/ja012009m

  日期：2001.12.19

  The synthesis of 1,1-disubstituted alkenes typically involves reactions that lack atom economy such as olefination protocols. The use of various ruthenium complexes to effect the addition of terminal alkynes to alkenes is explored as an atom economical strategy. Two new ruthenium complexes have been discovered that effect this reaction at ambient temperature, cyclopentadienyl ruthenium (triphenylphosphine) camphorsulfonate and cyclopentadienylruthenium tris(acetonitrile) hexafluorophosphate. Using these complexes as catalysts, reactions proceed at ambient temperature in acetone or DMF, respectively. Regioselectivity favoring the formation of a 1,1-disubstituted over a 1,2-disubstituted alkene typically ranges from 9:1 to > 25: 1. The reaction demonstrates extraordinary chemoselectivity-even di- and trisubstituted alkenes such as present in the products do not compete with the starting monosubstituted alkene. Free hydroxyl groups a well as silyl and PMB ethers are tolerated as are ketones, esters, and amides. The mechanism of the reaction is believed to invoke formation of a metallacyclopentene. To account for the chemo- and regioselectivity, the initial formation of the metallacycle is believed to be reversible. While formation of the 2,5-disubstituted ruthenacyclopentene, which produces the linear product, is believed to be kinetically preferred. the rate of beta -hydrogen elimination from the 2,4-disubstituted ruthenacyclopentene, which produces the branched product, is believed to be faster. Thus, the competition between the rate of beta -hydrogen elimination and cycloreversion rationalizes the results.