(1E,4E)-1-phenyl-1,4-hexadien-3-one | 91897-73-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (1E,4E)-1-phenyl-1,4-hexadien-3-one
• 英文别名: (1E,4E)-1-phenylhexa-1,4-dien-3-one
• CAS: 91897-73-3
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: GXRIMDUAAIHQMA-QAZUQVFVSA-N

物化性质

• 沸点：
  290.4±19.0 °C(Predicted)
• 密度：
  1.009±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1E,4E)-1-phenyl-1,4-hexadien-3-one 在 Schwartz's reagent 、 四氯化钛 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.5h， 生成
  参考文献：
  名称：

  Novel CuBr·SMe₂Catalyzed Conjugate Addition of 3-Trimethylsilyl-1-propenylzirconocene to Divinylketones. Stereoselective Synthesis of Poly­substituted Cyclohexanones

  摘要：

  催化量的CuBr·SMe2存在下，(E)-3-三甲基硅基-1-丙烯基锆杂环戊二烯与(E,E)-二乙烯基酮在温和条件下进行共轭加成，以良好产率得到含(E)-α,β-不饱和羰基部分的(E)-烯丙基硅烷。这些化合物经TiCl4处理后可发生高度立体控制性的硅辅助分子内环化反应，生成多取代环己酮。

  DOI：

  10.1055/s-2003-37525
• 作为产物：
  描述：

  乙酸烯丙酯 、 肉桂醇 在 tris(triphenylphosphine)ruthenium(II) chloride 一氧化碳 、 potassium carbonate 作用下， 以 四氢呋喃 为溶剂， 150.0 ℃ 、980.59 kPa 条件下， 反应 12.0h， 以27%的产率得到(1E,4E)-1-phenyl-1,4-hexadien-3-one
  参考文献：
  名称：

  Ruthenium-catalyzed allylation of primary alcohols by allylic acetates: a novel synthesis of .alpha.,.beta.-unsaturated ketones

  摘要：

  Certain ruthenium complexes show high catalytic activity in the synthesis of alpha,beta-unsaturated ketones from primary alcohols and allylic acetates. Here, pi-allylruthenium intermediates apparently operate as nucleophiles rather than as electrophiles.Among the carbon-carbon bond forming reactions promoted by transition-metal complexes, allylic alkylations, especially those catalyzed by palladium complexes, have been extensively studied and have been successfully applied in organic synthesis.1 In contrast, comparatively little is known about alkylation reactions involving pi-allylruthenium intermediates, despite the current interest in the synthesis of pi-allylruthenium complexes.2In the course of studies of catalysis by ruthenium complexes,3 we found that pi-allylruthenium intermediates act as nucleophiles rather than as electrophiles in reactions with aldehydes to give homoallylic alcohols.4 This reactivity is quite different from that of pi-allylpalladium complexes which generally act as electrophiles.5 Because many biologically important natural products possess an enone functionality, and because the synthesis of such compounds has been the target of much effort over the last decade,6 we attempted to apply ruthenium catalysis to the synthesis of enones. Therefore, in this paper, we describe a novel synthesis of alpha,beta-unsaturated ketones from primary alcohols and allylic acetates via pi-allylruthenium intermediates (eq 1).

  DOI：

  10.1021/jo00002a003

文献信息

• Catalytic asymmetric allylations of achiral and chiral aldehydes via BINOL–Zr complex
  作者：Michio Kurosu、Miguel Lorca

  DOI：10.1016/s0040-4039(02)00139-9

  日期：2002.3

  The complex generated from BINOL, Zr(OtBu)4, and 4 Å MS in toluene–pivalonitrile is very effective for catalytic asymmetric allylation of aldehydes using allyltributyltin. The reactions of achiral aldehyde under these conditions are completed within 3 h using 10–20 mol% of the complex at −20°C. The ees of homoallylic alcohols can be enhanced up to 98% via the tandem asymmetric allylation–Oppenauer

  由甲苯，新戊腈中的BINOL，Zr（O t Bu）4和4ÅMS生成的络合物对于使用烯丙基三丁基锡催化醛的催化不对称烯丙基化非常有效。在20°C下，使用10–20 mol％的配合物，可在3小时内完成这些条件下的非手性醛的反应。通过串联不对称烯丙基化-Oppenauer氧化可将均丙醇的ee提高至98％。对β-烷氧基醛的这些条件的范围和局限性进行了广泛的研究。
• Gold-Catalyzed Tandem Cyclization of Dienol Silyl Ethers for the Preparation of Bicyclo[4.3.0]nonane Derivatives
  作者：Hiroyuki Kusama、Yusuke Karibe、Yuji Onizawa、Nobuharu Iwasawa

  DOI：10.1002/anie.201001061

  日期：——

  Tandem bicycle: A gold‐catalyzed geminal carbo‐functionalization reaction of 3‐siloxy‐1,3‐dien‐8‐ynes proceeded smoothly to give bicyclo[4.3.0]nonanes stereoselectively through ring expansion of the bicyclic carbene complex intermediates. The product configuration was different from that of the thermal Diels–Alder adduct.

  双人自行车：通过3-双环卡宾配合物中间体的扩环反应，金催化的3-甲硅烷氧基-1,3-二烯基-8-炔烃的双官能[4.3.0]壬烷顺利进行。产品结构与Diels-Alder热加合物的结构不同。
• Asymmetric Ni-Catalyzed Conjugate Allylation of Activated Enones
  作者：Joshua D. Sieber、James P. Morken

  DOI：10.1021/ja710922h

  日期：2008.4.1

  The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester, allylB(pin), is described. This reaction is highly effective with dialkylidene ketones and favors the allylation of the benzylidene site in nonsymmetric substrates. The reaction appears to proceed by conversion of the dialkylidene ketone substrate to an unsaturated pi-allyl complex (I), followed by reductive elimination

  描述了镍催化的烯丙基硼酸频哪醇酯烯丙基 B(pin) 的对映选择性加成。该反应对二亚烷基酮非常有效，并有利于非对称底物中亚苄基位点的烯丙基化。该反应似乎是通过将二亚烷基酮底物转化为不饱和的 pi-烯丙基络合物 (I)，然后进行还原消除来进行的。当使用手性配体 14 时，一系列底物的对映选择性范围为 91% 至 94% ee。
• Catalytic Conjugate Addition of Allyl Groups to Styryl-Activated Enones
  作者：Joshua D. Sieber、Shubin Liu、James P. Morken

  DOI：10.1021/ja067878w

  日期：2007.2.1

  Conjugate addition of pinacolato(allyl)boron to benzylidenealkylidene ketones is remarkably facile when catalyzed by Ni(0) and Pd(0) complexes. Simple enones are inert to the reaction conditions, suggesting a significant activating effect by the auxiliary benzylidene unit. A comparison of different catalysts and substrates is provided, as is a mechanistic rationale, and an example of asymmetric catalysis

  当由 Ni(0) 和 Pd(0) 配合物催化时，频哪醇（烯丙基）硼与亚苄基亚烷基酮的共轭加成非常容易。简单的烯酮对反应条件是惰性的，表明辅助亚苄基单元具有显着的活化作用。提供了不同催化剂和底物的比较，以及机械原理和不对称催化的示例。
• Steric Tuning of Silylacetylenes and Chiral Phosphine Ligands for Rhodium-Catalyzed Asymmetric Conjugate Alkynylation of Enones
  作者：Takahiro Nishimura、Xun-Xiang Guo、Nanase Uchiyama、Taisuke Katoh、Tamio Hayashi

  DOI：10.1021/ja710540s

  日期：2008.2.6

  Rhodium-catalyzed asymmetric conjugate alkynylation of α,β-unsaturated ketones giving β-alkynylketones took place in high yields with high enantioselectivity. The reaction was realized by use of (triisopropylsilyl)acetylene combined with (R)-DTBM-segphos as a chiral phosphine ligand, where the sterically bulky substituents on the silicon and phosphorus atoms suppress the alkyne dimerization.

  铑催化的 α,β-不饱和酮的不对称共轭炔基化以高产率和高对映选择性发生 β-炔基酮。该反应是通过使用（三异丙基甲硅烷基）乙炔与（R）-DTBM-segphos 结合作为手性膦配体来实现的，其中硅和磷原子上的空间庞大的取代基抑制炔二聚化。