1,3-dimethyl-1-(4-methoxyphenyl)allene | 155096-10-9

• 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: 1,3-dimethyl-1-(4-methoxyphenyl)allene
• 英文别名: 1-methoxy-4-(penta-2,3-dien-2-yl)benzene
• CAS: 155096-10-9
• 化学式: C₁₂H₁₄O
• 分子量: 174.243
• InChiKey: FAQYEFCMQFZHIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,2,3,4,5-五甲基环戊二烯 、 1,3-dimethyl-1-(4-methoxyphenyl)allene 在 2,6-二叔丁基吡啶 、 (CH₃C₆H₄)3NSbF₆ 作用下， 以 乙腈 为溶剂， 反应 1.08h， 以19%的产率得到
  参考文献：
  名称：

  Cation Radical Catalyzed Diels-Alder Reaction of Electron-Rich Allenes

  摘要：

  The cation radical catalyzed cycloaddition of electron-rich arylallenes 1a-e with 1,2,3,4,5-pentamethylcyclopentadiene (2a) afforded the Diels-Alder products 3 and 4 at 0 degrees C in 5 min with a high chemoselectivity, facial selectivity, and stereoselectivity. From the results of various mechanistic tests, it is inferred that the electron transfer induced reaction proceeds via a [3 + 2] pathway by cycloaddition of the diene cation radical to a neutral allene 1 exhibiting a rather short chain length. However, with electron-withdrawing substituents at the remote end of the allene functionality, the cycloaddition is only a minor reaction path. With diarylallene 1f and diene 2a, or 2b, no cycloaddition but formation of products 7 and d(1)-7 occurred. It is concluded that distonic cation radicals may be intermediates in a stepwise formal Diels-Alder reaction induced by electron transfer.

  DOI：

  10.1021/jo00130a022
• 作为产物：
  描述：

  (E,Z)-2,3-dimethyl-2-(4-methoxyphenyl)-1,1-dibromocyclopropane 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 1.5h， 以78%的产率得到1,3-dimethyl-1-(4-methoxyphenyl)allene
  参考文献：
  名称：

  Cation Radical Catalyzed Diels-Alder Reaction of Electron-Rich Allenes

  摘要：

  The cation radical catalyzed cycloaddition of electron-rich arylallenes 1a-e with 1,2,3,4,5-pentamethylcyclopentadiene (2a) afforded the Diels-Alder products 3 and 4 at 0 degrees C in 5 min with a high chemoselectivity, facial selectivity, and stereoselectivity. From the results of various mechanistic tests, it is inferred that the electron transfer induced reaction proceeds via a [3 + 2] pathway by cycloaddition of the diene cation radical to a neutral allene 1 exhibiting a rather short chain length. However, with electron-withdrawing substituents at the remote end of the allene functionality, the cycloaddition is only a minor reaction path. With diarylallene 1f and diene 2a, or 2b, no cycloaddition but formation of products 7 and d(1)-7 occurred. It is concluded that distonic cation radicals may be intermediates in a stepwise formal Diels-Alder reaction induced by electron transfer.

  DOI：

  10.1021/jo00130a022

文献信息

• Hydromagnesiation of 1,3‐Enynes by Magnesium Hydride for Synthesis of Tri‐ and Tetra‐substituted Allenes
  作者：Bin Wang、Yihang Li、Jia Hao Pang、Kohei Watanabe、Ryo Takita、Shunsuke Chiba

  DOI：10.1002/anie.202012027

  日期：2021.1.4

  A protocol for regio‐controlled hydromagnesiation of 1,3‐enynes was developed using magnesium hydride that is generated in situ by solvothermal treatment of sodium hydride (NaH) and magnesium iodide (MgI2) in THF. The resulting allenylmagnesium species could be converted into tri‐ and tetra‐substituted allenes by subsequent treatment with various carbon‐ and silicon‐based electrophiles with the aid

  通过使用氢化钠（NaH）和碘化镁（MgI 2）在THF中的溶剂热处理原位生成的氢化镁，开发了一种用于1,3-炔烃的区域控制加氢放大的方案。通过随后使用各种碳基和硅基亲电试剂，借助CuCN作为催化剂，可以将所得的烯基镁物质转化为三取代和四取代的烯。