trans,trans-1,3-diethenyl-2-(2-propynyl)cyclohexane | 230635-84-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: trans,trans-1,3-diethenyl-2-(2-propynyl)cyclohexane
• CAS: 230635-84-4
• 化学式: C₁₃H₁₈
• 分子量: 174.286
• InChiKey: JDVFIUFNTRZRDI-ITGUQSILSA-N

反应信息

• 作为反应物：
  描述：

  trans,trans-1,3-diethenyl-2-(2-propynyl)cyclohexane 、 alkaline earth salt of/the/ methylsulfuric acid 在 十二/十四烷基二甲基氧化胺 作用下， 以 二氯甲烷 为溶剂， 反应 4.75h， 以88%的产率得到(1R*,2S*,6S*,7S*)-6-ethenyltricyclo[7.3.0.0^2,7]dodec-9-en-11-one
  参考文献：
  名称：

  Stereoselectivity in the intramolecular Pauson-Khand reaction: Towards a simple predictive model

  摘要：

  The major product in the intramolecular Pauson-Khand reaction of 3,4-disubstituted 1,6-heptenynes to form bicyclo[3.3.0]octenones is highly dependent on the relative configurations of the two stereocenters of the substrate. For example, cycloaddition of the "syn,syn" stereoisomer of 3,5-dimethyl-4-propargyl-1,6-heptadiene gives predominantly an enone containing both substituents in more hindered endo orientations; the "syn,anti" stereoisomer, upon reaction across the "syn" linkage similarly gives mostly endo product, but upon reaction across the "anti" portion of the molecule affords almost exclusively an enone in which the C6 methyl group possesses exo stereochemistry. Parallel results obtain from enynes built upon cyclohexane frameworks. Calculated energies of pre-cycloaddition enynes, metallacycles presumed to be the penultimate intermediates in the cyclization mechanism, and the final products are examined in order to develop a reasonable predictive model. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00343-9
• 作为产物：
  描述：

  trans-3-ethenyl-2-(2-propynyl)cyclohexanone 在 Amberlite IR-120(plus) ion exchange resin 、 sodium hydride 作用下， 以 水 、 二甲基亚砜 为溶剂， 反应 21.0h， 生成 trans,trans-1,3-diethenyl-2-(2-propynyl)cyclohexane
  参考文献：
  名称：

  Stereoselectivity in the intramolecular Pauson-Khand reaction: Towards a simple predictive model

  摘要：

  The major product in the intramolecular Pauson-Khand reaction of 3,4-disubstituted 1,6-heptenynes to form bicyclo[3.3.0]octenones is highly dependent on the relative configurations of the two stereocenters of the substrate. For example, cycloaddition of the "syn,syn" stereoisomer of 3,5-dimethyl-4-propargyl-1,6-heptadiene gives predominantly an enone containing both substituents in more hindered endo orientations; the "syn,anti" stereoisomer, upon reaction across the "syn" linkage similarly gives mostly endo product, but upon reaction across the "anti" portion of the molecule affords almost exclusively an enone in which the C6 methyl group possesses exo stereochemistry. Parallel results obtain from enynes built upon cyclohexane frameworks. Calculated energies of pre-cycloaddition enynes, metallacycles presumed to be the penultimate intermediates in the cyclization mechanism, and the final products are examined in order to develop a reasonable predictive model. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(99)00343-9