4,4-dimethylhepta-1,6-diyne | 148181-34-4

• 分子结构分类: 有机化合物 - 乙炔化物
• 英文名称: 4,4-dimethylhepta-1,6-diyne
• 英文别名: 4,4-dimethyl-1,6-heptadiyne
• CAS: 148181-34-4
• 化学式: C₉H₁₂
• 分子量: 120.194
• InChiKey: CDQBIWFUOSRDAK-UHFFFAOYSA-N

物化性质

• 沸点：
  149.2±13.0 °C(Predicted)
• 密度：
  0.830±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  dimethyl(phenyl)silyllithium 、 4,4-dimethylhepta-1,6-diyne 在 甲基锂 作用下， 生成 (Z)-1-methylidene-4,4-dimethyl-2-methylidenecyclopentane
  参考文献：
  名称：

  Silyl-cupration of an acetylene followed by ring-formation

  摘要：

  烷炔1a–e经历硅烷-铜化反应后进行环化，而烷炔1f–1h在另一种电亲和位点与硅烷-铜试剂的反应速度更快，烷炔1i、1j和17等反应给出的环状产物产率相对较低。环的形成在这里是不太常见的，不是特别有利的途径。

  DOI：

  10.1039/a809813a
• 作为产物：
  描述：

  1--4,4-dimethylhepta-1,6-diyne 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.5h， 以85%的产率得到4,4-dimethylhepta-1,6-diyne
  参考文献：
  名称：

  Silyl-cupration of an acetylene followed by ring-formation

  摘要：

  烷炔1a–e经历硅烷-铜化反应后进行环化，而烷炔1f–1h在另一种电亲和位点与硅烷-铜试剂的反应速度更快，烷炔1i、1j和17等反应给出的环状产物产率相对较低。环的形成在这里是不太常见的，不是特别有利的途径。

  DOI：

  10.1039/a809813a

文献信息

• Divergent total syntheses of five illudalane sesquiterpenes and assignment of the absolute configuration
  作者：Zhixiong Zeng、Yifan Zhao、Yandong Zhang

  DOI：10.1039/c9cc00933g

  日期：——

  Concise, divergent total syntheses of five bioactive illudalane sesquiterpenes have been achieved. Our synthesis features an intermolecular [2+2+2] cycloaddition, and a lactone-directed aromatic C–H oxygenation to generate a temporary phenolic hydroxyl group which enables regioselective methylation. Furthermore, the absolute configuration of radulactone was assigned by chemical synthesis.

  五个生物活性的伊杜鲁烷倍半萜的简明，不同的总合成方法已经实现。我们的合成具有分子间[2 + 2 + 2]环加成和内酯导向的芳香族C–H氧合作用，以生成临时的酚羟基，从而实现区域选择性的甲基化。此外，通过化学合成确定了Radulactone的绝对构型。
• Studies on Chromium(0)-Mediated Three Component Cycloaddition Reactions
  作者：James H. Rigby、Charles R. Heap、Namal C. Warshakoon

  DOI：10.1016/s0040-4020(99)01113-8

  日期：2000.4

  A novel chromium(0)-promoted three-component alkyne–triene higher-order cycloaddition process is presented. The transformation features tethered alkynes participating in a tandem [6π+2π], [6π+2π] cycloaddition event with cyclic trienes serving as the third reactant. Isomerically homogeneous products possessing five rings and six stereogenic centers are isolated from this reaction in good to excellent

  提出了一种新型的铬（0）促进的三组分炔烃-三烯高阶环加成工艺。该转化的特征在于拴系炔烃参与串联[6π+2π]，[6π+2π]环加成事件，其中环状三烯充当第三种反应物。从该反应中以良好至优异的产率分离出具有五个环和六个立体异构中心的异构均质产物。
• Synthesis of 4,4-Dimethyl-1,6-heptadiyne and Other Neopentylene-Tethered (NPT) 1,6-Diynes
  作者：Amir Tavakoli、Gregory B. Dudley

  DOI：10.1021/acs.joc.2c00110

  日期：2022.5.6

  target-oriented synthesis. Ring-opening fragmentation of dimedone (and alkylation) produces alkyne-tethered β-keto esters 6. One-pot dehydration with optional saponification produces diyne monoester 15 or monoacid 3, which can be further functionalized using traditional alkyne substitution chemistry and/or carboxylate manipulations. For example, copper-catalyzed decarboxylation of acid 3 provides 4,4-dimethyl-1

  描述了用于制备新戊烯系 (NPT) 1,6-二炔的两种不同且互补的方法。这些 NPT 1,6-二炔是有价值的 π-系统，可用于反应发现和靶向合成的构建块。二甲酮的开环断裂（和烷基化）产生炔烃连接的 β-酮酯6。可选皂化的一锅脱水产生二炔单酯15或单酸3，可以使用传统的炔烃取代化学和/或羧酸盐操作进一步对其进行功能化。例如，酸3的铜催化脱羧产生4,4-二甲基-1,6-庚二炔 ( 1)，现在在 ca。来自二甲酮的四步产率为 76%。使用 Zard 裂解化学的补充方法将烷基化 β-酮酯转化为相应的单烷基化 NPT 1,6-二炔。本文指出了取代的 NPT 1,6-二炔在靶向合成中的效用。
• Synthesis of 4,4-Dimethyl-1,6-heptadiyne and Alcyopterosin O
  作者：Amir Tavakoli、Gregory B. Dudley

  DOI：10.1021/acs.orglett.0c03356

  日期：2020.11.20

  A four-step synthesis of 4,4-dimethyl-1,6-heptadiyne and an associated five-step synthesis of alcyopterosin O, an illudalane sesquiterpene natural product, are described starting from commercially available dimedone. The process features C-C bond-cleaving fragmentation and elimination methods for making alkynes, and it proceeds by way of nonsymmetrical diynes that are themselves valuable synthetic building blocks, as exemplified by the synthesis of alcyopterosin O.
• Microwave-Mediated Nickel-Catalyzed Cyclotrimerization Reactions:  Total Synthesis of Illudinine
  作者：Jesse A. Teske、Alexander Deiters

  DOI：10.1021/jo7020955

  日期：2008.1.1

  [GRAPHICS]Rapid and efficient [2 + 2 + 2] cyclotrimerization reactions were discovered through the application of microwave irradiation in conjunction with a Ni(CO)(2)(PPh3)(2) catalyst. This enables the facile construction of highly substituted indane, isoindoline, and tetraline core structures. The developed microwave-mediated Ni-catalyzed cyclotrimerization reaction was employed as the key step in a concise synthesis of the isoquinoline natural product illudinine. This represents the first example of a Ni-catalyzed cyclotrimerization reaction in total synthesis.