7-methylene-4-tridecen-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-methylene-4-tridecen-2-one
• 英文别名: (E)-7-methylidenetridec-4-en-2-one
• 化学式: C₁₄H₂₄O
• 分子量: 208.344
• InChiKey: YGQDVWZDKGTHGF-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  15
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  5-已烯-2-酮 、 1-辛炔 在 (cyclooctadienyl)(cyclopentadienyl)ruthenium chloride 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 4,7-tetradecadien-2-one 、 7-methylene-4-tridecen-2-one
  参考文献：
  名称：

  A Ru Catalyzed Addition of Alkenes to Alkynes

  摘要：

  The potential of the Alder ene reaction which possesses high atom economy is not realized because of limitations of scope and selectivity. Thus, the thermal bimolecular addition of unactivated alkenes to unactivated alkynes has not been reported. This addition now becomes possible through the advent of ruthenium catalysis. Several ruthenium complexes are effective including (PhOCH(3))(Ph(3)P)RuCl2, (p-cymene)(Ph(3)P)RuCl2, (p-cymene)[(C4H9)(3)P]RuCl2, and CpRu(COD)Cl, but the latter gives the highest conversions and regioselectivities. The reaction best proceeds in aqueous DMF at 100 degrees C or methanol at reflux. Both internal and terminal alkynes react. Monosubstituted alkenes are required. The reaction exhibits extraordinary chemoselectivity and control of product double bond geometry. A mechanism envisioning formation of a ruthenacyclopentene accounts for the experimental observations.

  DOI：

  10.1021/ja00107a005

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.
• Ruthenium-catalyzed addition of alkenes to acetylenes
  作者：Barry M. Trost、Adriano Indolese

  DOI：10.1021/ja00063a064

  日期：1993.5