4,5-Diethylideneocta-2,6-diyne | 58873-38-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4,5-Diethylideneocta-2,6-diyne
• 英文别名: 4,5-di(ethylidene)octa-2,6-diyne
• CAS: 58873-38-4
• 化学式: C₁₂H₁₄
• 分子量: 158.24
• InChiKey: DLCOALBJQHQANI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  苯硅烷 、 4,5-Diethylideneocta-2,6-diyne 在 C₄₀H₄₈Cl₂FeN₂ 、 乙基溴化镁 作用下， 以 2-甲基四氢呋喃 、 四氢呋喃 为溶剂， 生成 、
  参考文献：
  名称：

  Iron‐Catalyzed Allylic C(sp³)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity

  摘要：

  The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp³)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp³)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp³)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies.

  DOI：

  10.1002/anie.202402044
• 作为产物：
  描述：

  2,4-己二炔 在 bis-triphenylphosphine-palladium(II) chloride 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 碘 、 zinc(II) chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 4,5-Diethylideneocta-2,6-diyne
  参考文献：
  名称：

  Iron‐Catalyzed Allylic C(sp³)−H Silylation: Spin‐Crossover‐Efficiency‐Determined Chemoselectivity

  摘要：

  The nuanced role of spin effects remains a critical gap in designing proficient open‐shell catalysts. This study elucidates an iron‐catalyzed allylic C(sp³)−H silylation/alkyne hydrosilylation reaction, in which the spin state of the open‐shell iron catalyst dictates the reaction kinetics and pathway. Specifically, spin crossover led to alkyne hydrosilylation, whereas spin conservation resulted in a novel allylic C(sp³)−H silylation reaction. This chemoselectivity, governed by the spin‐crossover efficiency, reveals an unexpected dimension in spin effects and a first in the realm of transition‐metal‐catalyzed in situ silylation of allylic C(sp³)−H bonds, which had been previously inhibited by the heightened reactivity of alkenes in hydrosilylation reactions. Furthermore, this spin crossover can either accelerate or hinder the reaction at different stages within a single catalytic reaction, a phenomenon scarcely documented. Moreover, we identify a substrate‐assisted C−H activation mechanism, a departure from known ligand‐assisted processes, offering a fresh perspective on C−H activation strategies.

  DOI：

  10.1002/anie.202402044