2-(2-ethynyl-benzyl)-2-(2-methyl-allyl)-malonic acid dimethyl ester | 1187458-51-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(2-ethynyl-benzyl)-2-(2-methyl-allyl)-malonic acid dimethyl ester
• 英文别名: dimethyl 2-(2-ethynylbenzyl)-2-(2-methylallyl)malonate；Dimethyl 2-[(2-ethynylphenyl)methyl]-2-(2-methylprop-2-enyl)propanedioate；dimethyl 2-[(2-ethynylphenyl)methyl]-2-(2-methylprop-2-enyl)propanedioate
• CAS: 1187458-51-0
• 化学式: C₁₈H₂₀O₄
• 分子量: 300.354
• InChiKey: BENCWFFGMRUEMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(2-ethynyl-benzyl)-2-(2-methyl-allyl)-malonic acid dimethyl ester 在 C₃₁H₃₇AuN₃O₃⁽²⁺⁾*F₆Sb^(1-) 作用下， 以 二氯甲烷-D2 为溶剂， 生成 2a-methyl-2a,3,6,7,8,9-hexahydro-2H,5H-benzo[a]cyclobuta[c]cycloheptene-4,4-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  环丁烯在金（i）催化的1,6-炔烃骨架重排中的作用† ‡

  摘要：

  在炔烃上带有给电子取代基的1，6-烯炔经历金（I）催化的单裂解骨架重排，而具有吸电子取代基的底物选择性地演化为双裂解重排。理论计算为这些作用提供了定性的理论依据，并暗示涉及双环[3.2.0]庚-5-烯作为中间体。我们提供了第一个X射线结构证据，证明该类产物在1,6-烯炔的环异构化中的形成。

  DOI：

  10.1039/c2ob25419k
• 作为产物：
  描述：

  dimethyl (2-methyl-2-propenyl)-propanedioate 、 1-(溴甲基)-2-乙炔基苯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 以86%的产率得到2-(2-ethynyl-benzyl)-2-(2-methyl-allyl)-malonic acid dimethyl ester
  参考文献：
  名称：

  Cyclobutenes作为金（I）催化的1,8-烯炔的环异构化中的可分离中间体

  摘要：

  Abstractmagnified imageThe gold(I)‐catalysed isomerisation of 1,8‐enynes allows the efficient synthesis of functionalised bicyclo[5.2.0]nonenes. Notably, these cyclobutenes derivatives can be isolated as reactive intermediates that could undergo subsequent gold(I)‐catalysed transformations such as isomerisation, fragmentation or ene reaction to furnish more structurally complex products. This study also provides useful information related to the mechanism leading to metathesis‐type derivatives, examples of which were shown to be produced, in the present case, by a gold(I)‐catalysed ring fragmentation of the cyclobutene moiety.

  DOI：

  10.1002/adsc.200900056

文献信息

• Cyclobutenes as Isolable Intermediates in the Gold(I)-Catalysed Cycloisomerisation of 1,8-Enynes
  作者：Yann Odabachian、Fabien Gagosz

  DOI：10.1002/adsc.200900056

  日期：2009.2

  Abstractmagnified imageThe gold(I)‐catalysed isomerisation of 1,8‐enynes allows the efficient synthesis of functionalised bicyclo[5.2.0]nonenes. Notably, these cyclobutenes derivatives can be isolated as reactive intermediates that could undergo subsequent gold(I)‐catalysed transformations such as isomerisation, fragmentation or ene reaction to furnish more structurally complex products. This study also provides useful information related to the mechanism leading to metathesis‐type derivatives, examples of which were shown to be produced, in the present case, by a gold(I)‐catalysed ring fragmentation of the cyclobutene moiety.
• The role of cyclobutenes in gold(i)-catalysed skeletal rearrangement of 1,6-enynes
  作者：Ana Escribano-Cuesta、Patricia Pérez-Galán、Elena Herrero-Gómez、Masaki Sekine、Ataualpa A. C. Braga、Feliu Maseras、Antonio M. Echavarren

  DOI：10.1039/c2ob25419k

  日期：——

  electron-donating substituents at the alkyne undergo gold(I)-catalysed single cleavage skeletal rearrangement, whereas substrates with electron-withdrawing substituents evolve selectively to double cleavage rearrangement. Theoretical calculations provide a qualitative rationale for these effects, and suggest that bicyclo[3.2.0]hept-5-enes are involved as intermediates. We provide the first X-ray structural evidence

  在炔烃上带有给电子取代基的1，6-烯炔经历金（I）催化的单裂解骨架重排，而具有吸电子取代基的底物选择性地演化为双裂解重排。理论计算为这些作用提供了定性的理论依据，并暗示涉及双环[3.2.0]庚-5-烯作为中间体。我们提供了第一个X射线结构证据，证明该类产物在1,6-烯炔的环异构化中的形成。