(E,E)-1-phenyl-2,5-dimethyl-1,4-pentadien-3-one | 217076-66-9

• 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: (E,E)-1-phenyl-2,5-dimethyl-1,4-pentadien-3-one
• 英文别名: (E,E)-2-methyl-1-phenylhexa-1,4-dien-3-one；(1E,4E)-2-methyl-1-phenylhexa-1,4-dien-3-one
• CAS: 217076-66-9
• 化学式: C₁₃H₁₄O
• 分子量: 186.254
• InChiKey: OFXFORQZLRYINW-LRPGZYIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.15
• 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：

  (E,E)-1-phenyl-2,5-dimethyl-1,4-pentadien-3-one 在 三氟甲磺酸三甲基硅酯 、 3-((3,5-bis(trifluoromethyl)phenyl)amino)-4-(((S)-1-((R)-2-(4-fluorophenyl)-2-methylpyrrolidin-1-yl)-3,3-dimethyl-1-oxobutan-2-yl)amino)cyclobut-3-ene-1,2-dione 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以79%的产率得到2,4-dimethyl-3-phenylcyclopenten-1-one
  参考文献：
  名称：

  氢键供体/路易斯酸共催化对映选择性质子转移未活化二烯酮的不对称纳扎罗夫环化

  摘要：

  我们报道了手性氢键供体与甲硅烷基路易斯酸共同催化的对映选择性纳扎罗夫环化。所开发的转化可以从各种简单的未活化二烯酮中获得高水平对映选择性（高达 95% ee）的三取代环戊烯酮。动力学和机理研究与可逆 4π 电环化 C−C 键形成步骤一致，随后以速率和对映体决定质子转移作为催化模式。

  DOI：

  10.1002/adsc.202000831
• 作为产物：
  描述：

  α-甲基肉桂醛 在 barium permanganate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (E,E)-1-phenyl-2,5-dimethyl-1,4-pentadien-3-one
  参考文献：
  名称：

  Ionic Hydrogenation of Oxyallyl Intermediates: The Reductive Nazarov Cyclization

  摘要：

  Cyclization of tri- and tetrasubstituted dienones 1 under Lewis acidic conditions in the presence of triethylsilane led to formation of either silyl enol ethers 6 or cyclopentanones 7 in good to excellent yields, depending on work-up conditions. The proposed mechanism involves initial Nazarov cyclization to give oxyallyl intermediates 5, which are intercepted via intermolecular transfer of hydride. The reactions proceeded cleanly with as little as 2 equiv. of silane and in most cases catalytic amounts of Lewis acid could be used. Trapping with Et3SiD occurs at the less substituted terminus in unsymmetrical cases. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00866-8

文献信息

• Regioselective Synthesis of Enones via a Titanium-Promoted Coupling of Unsymmetrical Alkynes with Weinreb Amides
  作者：Sajan Silwal、Ronald J. Rahaim

  DOI：10.1021/jo5014417

  日期：2014.9.5

  A modular titanium-promoted coupling of unsymmetrical internal alkynes with Weinreb amides is described. The coupling reaction takes place at room temperature and affords E-trisubstituted enones in moderate to good yields with high levels of regioselectivity. The system shows moderate chemoselectivity.
• Polymer-Mediated Reactions. A Nazarov-Like Cyclization
  作者：Michael Smith、Christopher Pavlik、Martha Morton、Michael Invernale、Ian Berghorn、Gregory Sotzing

  DOI：10.1055/s-0030-1261194

  日期：2011.9

  The polymer PEDOT+ mediates a Nazarov-like cyclization of dienones, in an heterogeneous system and in hydrocarbon solvents. The polymer-mediated reactions show clear differences in product formation when compared to the same reaction with tosic acid, or when compared to reports in the literature. Comparable or improved yields are observed, as well as the ability to give a Nazarov product in cases where treatment with acid fails to give cyclization, or leads to an undesirable rearrangement. In addition, the ability to recycle the polymer makes this a potentially useful protocol for an important organic chemical reaction.
• The reductive Nazarov cyclization
  作者：Sören Giese、F.G. West

  DOI：10.1016/s0040-4039(98)01934-0

  日期：1998.11

  Tri- and tetrasubstituted 1,4-dien-3-ones 1 were treated with Lewis acid in the presence of triethylsilane, furnishing either silyl enol ethers 4 or cyclopentanones 5 in good yields, depending upon work-up conditions. This reaction is presumed to occur through oxyallyl intermediate 3, which undergoes intermolecular hydride transfer and O-silylation to give 4. In most cases, only 2 equiv. of silane was required, and catalytic amounts of Lewis acid could be used. Trienone substrate 7 was found to undergo clean conversion to tricyclic ether 8, indicating fast capture of the oxyallyl intermediate by the pendant olefin. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Intermolecular Trapping of the Nazarov Intermediate: Domino Electrocyclization/[3+2] Cycloadditions with Allylsilanes
  作者：Sören Giese、Lars Kastrup、Dirk Stiens、Frederick G. West

  DOI：10.1002/1521-3773(20000602)39:11<1970::aid-anie1970>3.0.co;2-b

  日期：2000.6.2
• Asymmetric Nazarov Cyclizations of Unactivated Dienones by Hydrogen‐Bond‐Donor/Lewis Acid Co–Catalyzed, Enantioselective Proton‐Transfer
  作者：Jan B. Metternich、Martin Reiterer、Eric N. Jacobsen

  DOI：10.1002/adsc.202000831

  日期：2020.10.6

  cyclization catalyzed by chiral hydrogen‐bond‐donors in concert with silyl Lewis acids. The developed transformation provides access to tri‐substituted cyclopentenones in high levels of enantioselectivity (up to 95% e.e.) from a variety of simple unactivated dienones. Kinetic and mechanistic studies are consistent with a reversible 4π‐electrocyclization C−C bond‐forming step followed by rate‐ and enantio‐determining

  我们报道了手性氢键供体与甲硅烷基路易斯酸共同催化的对映选择性纳扎罗夫环化。所开发的转化可以从各种简单的未活化二烯酮中获得高水平对映选择性（高达 95% ee）的三取代环戊烯酮。动力学和机理研究与可逆 4π 电环化 C−C 键形成步骤一致，随后以速率和对映体决定质子转移作为催化模式。