4,4-dimethyl-3-((p-methoxybenzyl)oxy)-6-hepten-1-yne | 155693-48-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4,4-dimethyl-3-((p-methoxybenzyl)oxy)-6-hepten-1-yne
• 英文别名: 1-(4,4-dimethylhept-6-en-1-yn-3-yloxymethyl)-4-methoxybenzene
• CAS: 155693-48-4
• 化学式: C₁₇H₂₂O₂
• 分子量: 258.36
• InChiKey: MMHITJAAPOKDDX-UHFFFAOYSA-N

物化性质

• 沸点：
  350.4±42.0 °C(predicted)
• 密度：
  0.978±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 重原子数：
  19.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-3-((p-methoxybenzyl)oxy)-6-hepten-1-yne 在 正丁基锂 、 Pd(OAc)2[P(2-tolyl)3]2 作用下， 以 苯 为溶剂， 反应 9.83h， 生成
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  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.

  DOI：

  10.1021/ja00089a015
• 作为产物：
  描述：

  2,2-二甲基-4-戊烯醛 在 氢氧化钾 、 正丁基锂 、 potassium hydride 作用下， 反应 6.08h， 生成 4,4-dimethyl-3-((p-methoxybenzyl)oxy)-6-hepten-1-yne
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2- Dialkylidenecycloalkanes. 1

  摘要：

  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.

  DOI：

  10.1021/ja00089a015

文献信息

• A novel cycloalkylation of 1,6- and 1,7-enynes with stabilized pronucleophiles
  作者：Barry M. Trost、Lin Zhi、Katsuharu Imi

  DOI：10.1016/s0040-4039(00)76218-6

  日期：1994.2

  Formation of five and six membered rings simultaneously with addition of a functionalized side chain for further elaboration occurred upon exposing a 1:1 mixture of an enyne and a pronucleophile to a palladium catalyst derived from Pd(OAc)2 and a bidentate ligand.

  在将烯炔和亲核试剂的1：1混合物暴露于衍生自Pd（OAc）2和二齿配体的钯催化剂上时，同时形成五个和六个员环，同时添加官能化的侧链以进一步加工。