2-allyl-2-(3-oxo-1-phenylbutyl)malononitrile | 217433-39-1

• 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: 2-allyl-2-(3-oxo-1-phenylbutyl)malononitrile
• 英文别名: 5,5-dicyano-4-phenyl-7-octen-2-one；2-(1-Phenyl-3-oxobutyl)-2-allylmalononitrile；2-(3-oxo-1-phenylbutyl)-2-prop-2-enylpropanedinitrile
• CAS: 217433-39-1
• 化学式: C₁₆H₁₆N₂O
• 分子量: 252.316
• InChiKey: AJCCEJWYCIMWOR-UHFFFAOYSA-N

物化性质

• 熔点：
  64-65 °C
• 沸点：
  487.1±45.0 °C(Predicted)
• 密度：
  1.077±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  64.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  乙酰乙酸烯丙酯 、 苄烯丙二腈 在 2,2'-联吡啶 、 chloro(pentamethylcyclopentadienyl)ruthenium(II) tetramer 作用下， 以 二氯甲烷 为溶剂， 反应 120.0h， 以65%的产率得到2-allyl-2-(3-oxo-1-phenylbutyl)malononitrile
  参考文献：
  名称：

  通过有机金属钌催化形成耐空气的C–C键：涉及（C 5 Me 5）Ru或（C 5 H 5）Ru的多种催化途径对分子氧具有鲁棒性

  摘要：

  碳原子亲核试剂的钌催化取代，各种[2 + 2 + 2]环加成反应以及重氮化合物向炔烃的加成反应均在空气存在下进行。值得注意的是，各种催化歧管在通常被认为是禁止的条件下仍保持支撑。基于文献的稀有报道，我们表明基于衍生自（C 5 Me 5）Ru或（C 5 H 5）Ru部分的反应中间体的一系列有机金属转化是与空气相容的。

  DOI：

  10.1016/j.tetlet.2009.05.079

文献信息

• Palladium Catalyzed Regioselective β-Acetonation−α-Allylation of Activated Olefins in One Shot
  作者：Jae-Goo Shim、Hiroyuki Nakamura、Yoshinori Yamamoto

  DOI：10.1021/jo981719g

  日期：1998.11.1

  The reaction of certain activated olefins 4 with allyl acetoacetate 5 in the presence of catalytic amounts of Pd(PPh3)(4) (5 mol %) in THF at room temperature gave the corresponding beta-acetonated alpha-allylated double addition products 6 regioselectively in good to excellent yields. The nature of the electron-withdrawing group in activated olefins affected significantly the reactivity of substrates; at least one of two electron-withdrawing groups of 4 should be a CN group. A proposed mechanism for this unprecedented three-component coupling reaction involves oxa-pi-allyl-pi-allylpalladium intermediate 3a (or its synthetic equivalents 3b-d). The in situ generation of activated olefins 4, from the aldehyde 11 and malononitrile 12, followed by the palladium-catalyzed reaction with allyl acetoacetate 5 also worked well, producing the corresponding three-component coupling products in good yields. Furthermore, allyltributylstannane 13 and alpha-chloro acetone 14 could be used as the alpha-allylation and beta-acetonation components, respectively, instead of allyl acetoacetate 5. The scope and limitations of palladium-catalyzed regioselective beta-acetonation-alpha-allylation reaction of activated olefins are described.
• Ruthenium-Catalyzed Decarboxylative Insertion of Electrophiles
  作者：Chao Wang、Jon A. Tunge

  DOI：10.1021/ol050466s

  日期：2005.5.1

  A ruthenium complex, Cp*Ru(bipyridyl)CI, has been developed as a catalyst for the first regioselective tandem Michael addition-allylic alkylation of activated Michael acceptors. The net transformation is the decarboxylative insertion of Michael acceptors into allyl beta-ketoesters.
• Air-tolerant C–C bond formation via organometallic ruthenium catalysis: diverse catalytic pathways involving (C5Me5)Ru or (C5H5)Ru are robust to molecular oxygen
  作者：Lukáš Severa、Jan Vávra、Anna Kohoutová、Martina Čížková、Tereza Šálová、Jakub Hývl、David Šaman、Radek Pohl、Louis Adriaenssens、Filip Teplý

  DOI：10.1016/j.tetlet.2009.05.079

  日期：2009.8

  carbon pronucleophiles, various [2+2+2] cycloadditions, and addition of a diazo compound to an alkyne are shown to proceed in the presence of air. Notably diverse catalytic manifolds remain supported under conditions generally regarded as prohibitive. Building on rare reports from the literature we show that a range of organometallic transformations based on reaction intermediates derived from (C5Me5)Ru

  碳原子亲核试剂的钌催化取代，各种[2 + 2 + 2]环加成反应以及重氮化合物向炔烃的加成反应均在空气存在下进行。值得注意的是，各种催化歧管在通常被认为是禁止的条件下仍保持支撑。基于文献的稀有报道，我们表明基于衍生自（C 5 Me 5）Ru或（C 5 H 5）Ru部分的反应中间体的一系列有机金属转化是与空气相容的。