4,4-Dimethyl-1-ethoxyhept-7-en-1-yn-3-ol | 293313-71-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-Dimethyl-1-ethoxyhept-7-en-1-yn-3-ol
• CAS: 293313-71-0
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: WOVVNQAFFIQMDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.95
• 重原子数：
  13.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4,4-Dimethyl-1-ethoxyhept-7-en-1-yn-3-ol 在 dicobalt octacarbonyl 咪唑 作用下， 以 乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 96.0h， 生成 cis-5,5-Dimethyl-4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-3-[(ethyl)oxy]-4,5,6,6a-tetrahydro-2(1H)-pentalenone
  参考文献：
  名称：

  (Alkylthio)alkynes as Addends in the Co(0) Catalyzed Intramolecular Pauson-Khand Reaction. Substituent Driven Enhancements of Annulation Efficiency and Stereoselectivity

  摘要：

  与末端炔烃相比，（甲硫基）炔烃通常是热促进的、由Co2(CO)8催化的烯炔和炔炔的Pauson-Khand反应的优越底物，能够提供更高产率和增强的非对映选择性。还透露了依赖于使用2,2,2-三氟乙醇作为共溶剂的产率改善，以及对（乙氧基）炔烃的内选择性的明显偏好。

  DOI：

  10.1055/s-2000-6301
• 作为产物：
  描述：

  2,2-二甲基-4-戊烯醛 、 乙氧基乙炔 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 正庚烷 为溶剂， 反应 0.25h， 以93%的产率得到4,4-Dimethyl-1-ethoxyhept-7-en-1-yn-3-ol
  参考文献：
  名称：

  (Alkylthio)alkynes as Addends in the Co(0) Catalyzed Intramolecular Pauson-Khand Reaction. Substituent Driven Enhancements of Annulation Efficiency and Stereoselectivity

  摘要：

  与末端炔烃相比，（甲硫基）炔烃通常是热促进的、由Co2(CO)8催化的烯炔和炔炔的Pauson-Khand反应的优越底物，能够提供更高产率和增强的非对映选择性。还透露了依赖于使用2,2,2-三氟乙醇作为共溶剂的产率改善，以及对（乙氧基）炔烃的内选择性的明显偏好。

  DOI：

  10.1055/s-2000-6301

文献信息

• Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1
  作者：Barry M. Trost、Gerald J. Tanoury、Mark Lautens、Chuen Chan、David T. MacPherson

  DOI：10.1021/ja00089a015

  日期：1994.5

  Enhancing synthetic efficiency requires the development of synthetic reactions that, to the extent possible, are simple additions wherein everything else is required only in catalytic amounts. The Alder ene reaction constitutes a classical reaction that meets this requirement that has much unrealized potential. A transition-metal-catalyzed version helps to increase that potential by permitting this reaction to proceed under mild conditions. A significant benefit of transition metal catalysis is the feasibility of diverting the reaction along pathways not feasible under thermal conditions. The synthesis of 1,3-dienes rather than 1,4-dienes is a very important diversion because of the utility of 1,3-dienes as reaction partners in the Diels-Alder reaction, another highly atom economical process. A catalyst derived from palladium acetate cycloisomerizes 1,6- and 1,7-enynes to dialkylidenecyclopentanes and -cyclohexanes. 1,3-Diene formation is favored over the Alder ene process by both steric and electronic effects. The reaction is highly chemoselective-tolerating a wide diversity of functionality including hydroxyl groups, ketones, esters, alkynyl and enol ethers, alkynyl and vinyl silanes, and enones. Many of the substrates are available by palladium-catalyzed alkylation reactions-highlighting the effectiveness of palladium catalyzed methodology in organic synthesis. The atom-economical nature of these reactions combined with the Diels-Alder reaction permit butadiene and dimethyl propargylmalonate to be molded into a polyhydro-as-indacene. The mechanism of this reaction may involve a tautomerization of an enyne-Pd(+2) complex to a pallada(+4)cyclopentene intermediate as a key step.