1-chloro-1,5-bis(trimethylsilyl)-1,2-pentadien-4-yne | 1198424-83-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 1-chloro-1,5-bis(trimethylsilyl)-1,2-pentadien-4-yne
• CAS: 1198424-83-7
• 化学式: C₁₁H₁₉ClSi₂
• 分子量: 242.896
• InChiKey: HIWAVFGTDLDBHT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.55
• 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：

  1-chloro-1,5-bis(trimethylsilyl)-1,2-pentadien-4-yne 在 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 methoxy(penta-1,2-dien-4-yn-3-yl)(2,4,6-tri-tert-butylphenyl)phosphine
  参考文献：
  名称：

  钯催化的交叉偶联反应中的C，C-二乙炔基磷烯烃†

  摘要：

  已经研究了双-TMS取代的C，C-二乙炔磷化烯烃（A 2 PA）1在Sonogashira-Hagihara交叉偶联反应中的反应性。选择性的且在两个甲硅烷基的脱保护的连续1由空间体积的MES启用*这使得乙炔基团的反式与MES *更具反应性的，从而有利于选择性的和连续的联接件与iodoarenes。TMS保护的乙炔的原位转化为Cu（I）乙炔化物是合成过程中的关键步骤，并能够制备通过亚苯基间隔基连接的第一个二聚体A 2 PA。整个P C键的顺式-反式异构化是由叔胺引发的，仅在硝基苯基取代的A 2 PA情况下才观察到。光谱和电化学研究证明，引入的芳基是整个π系统的组成部分。

  DOI：

  10.1039/c1ob05705g
• 作为产物：
  描述：

  1,5-bis(trimethylsilyl)penta-1,4-diyn-3-ol 在 氯化亚砜 作用下， 以 乙醚 为溶剂， 以71%的产率得到1,5-bis(trimethylsilyl)-3-chloropenta-1,4-diyne
  参考文献：
  名称：

  C,C-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues

  摘要：

  A series of C,C-diacetylenic phosphaalkenes 1b-e has been prepared from 1-chloropenta-1,2-dien-4-ynes 6b-e in a reaction with Mes*PCl2 (Mes* = 2,4,6-(Bu-1)(3)Ph) in the presence of LDA. Under identical conditions, isomeric butadiyne-substituted phosphaalkenes 2e-f can be obtained from 3-chloropenta-1,4-diyiies 5c-f. The title compounds represent rare examples of diethynylethenes in which a constituting methylene has been replaced by a phosphorus center. The formation of both isomers can be rationalized by a common pathway that involves isomeric allenyllithium species. Spectroscopic, electrochemical, and theoretical investigations show that the phosphorus heteroatoms are an intrinsic part of the compounds' pi-systems and lead to decreased HOMO-LUMO gaps compared to those in all-carbon-based reference compounds.

  DOI：

  10.1021/jo901942u

文献信息

• Alternative Synthesis of A C,C-Diacetylenic Phosphaalkene
  作者：Elisabet Öberg、Sascha Ott

  DOI：10.1080/10426507.2012.743146

  日期：2013.1.1

  Bis(trimethylsilyl)-terminated C,C-diacetylenic phosphaalkene was prepared from Mes*PCl2 and a propargylic Grignard reagent that in turn was formed from 3-bromo-1,5-bis(trimethylsilyl)penta-1,4-diyne and Rieke-Mg.
• <i>C</i>,<i>C</i>-Diacetylenic Phosphaalkenes as Heavy Diethynylethene Analogues
  作者：Elisabet Öberg、Bernhard Schäfer、Xue-Li Geng、Jenny Pettersson、Qi Hu、Mikael Kritikos、Torben Rasmussen、Sascha Ott

  DOI：10.1021/jo901942u

  日期：2009.12.18

  A series of C,C-diacetylenic phosphaalkenes 1b-e has been prepared from 1-chloropenta-1,2-dien-4-ynes 6b-e in a reaction with Mes*PCl2 (Mes* = 2,4,6-(Bu-1)(3)Ph) in the presence of LDA. Under identical conditions, isomeric butadiyne-substituted phosphaalkenes 2e-f can be obtained from 3-chloropenta-1,4-diyiies 5c-f. The title compounds represent rare examples of diethynylethenes in which a constituting methylene has been replaced by a phosphorus center. The formation of both isomers can be rationalized by a common pathway that involves isomeric allenyllithium species. Spectroscopic, electrochemical, and theoretical investigations show that the phosphorus heteroatoms are an intrinsic part of the compounds' pi-systems and lead to decreased HOMO-LUMO gaps compared to those in all-carbon-based reference compounds.
• C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions
  作者：Elisabet Öberg、Xue-Li Geng、Marie-Pierre Santoni、Sascha Ott

  DOI：10.1039/c1ob05705g

  日期：——

  and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(I)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A2PA linked by a phenylene spacer. cis–transIsomerization across the PC bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A2PAs. The introduced

  已经研究了双-TMS取代的C，C-二乙炔磷化烯烃（A 2 PA）1在Sonogashira-Hagihara交叉偶联反应中的反应性。选择性的且在两个甲硅烷基的脱保护的连续1由空间体积的MES启用*这使得乙炔基团的反式与MES *更具反应性的，从而有利于选择性的和连续的联接件与iodoarenes。TMS保护的乙炔的原位转化为Cu（I）乙炔化物是合成过程中的关键步骤，并能够制备通过亚苯基间隔基连接的第一个二聚体A 2 PA。整个P C键的顺式-反式异构化是由叔胺引发的，仅在硝基苯基取代的A 2 PA情况下才观察到。光谱和电化学研究证明，引入的芳基是整个π系统的组成部分。