dec-5-ene-3,7-diyne-2,9-dione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: dec-5-ene-3,7-diyne-2,9-dione
• 英文别名: (Z)-dec-5-en-3,7-diyne-2,9-dione
• 化学式: C₁₀H₈O₂
• 分子量: 160.172
• InChiKey: ATEKRZOMGIHUOP-ARJAWSKDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1,6-bis(trimethylsilyl)-3(Z)-hexene-1,5-diyne 、 乙酰氯 在 三氯化铝 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以63%的产率得到dec-5-ene-3,7-diyne-2,9-dione
  参考文献：
  名称：

  Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity

  摘要：

  The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G* + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (Delta DeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.

  DOI：

  10.1021/jo001417q

文献信息

• Carbonyl- and Carboxyl-Substituted Enediynes:  Synthesis, Computations, and Thermal Reactivity
  作者：Burkhard König、Wolfgang Pitsch、Michael Klein、Rudolf Vasold、Matthias Prall、Peter R. Schreiner

  DOI：10.1021/jo001417q

  日期：2001.3.1

  The influence of electron-withdrawing groups (carbonyl and carboxyl) at the alkyne termini on the reactivity of enediynes was investigated by a combination of experimental and computational techniques. While the general chemical reactivity of such enediynes, especially if non-benzannelated, is increased markedly, the thermal cyclization, giving rise to Bergman cyclization products, is changed little relative to the parent enediyne system. This is evident from kinetic measurements and from density functional theory (DFT, BLYP/6-31G* + thermal corrections) computations of the experimental systems which show that the Bergman cyclization barriers slightly (3-4 kcal/mol) increase, in contrast to earlier theoretical predictions. The effect on the endothermicities is large (Delta DeltaH(r) = 7-12 kcal/mol). Hence, the increased reactivity of the substituted enediynes is entirely due to nucleophiles or radicals present in solution. This was demonstrated by quantitative experiments with diethylamine and tetramethyl piperidyl oxide (TEMPO) which both give fulvenes through 5-exo-dig cyclizations.