Z-3-ethyl-3-phenyl-4-(1-phenyl-propylidene)-oxetan-2-one | 1114455-09-2

• 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: Z-3-ethyl-3-phenyl-4-(1-phenyl-propylidene)-oxetan-2-one
• 英文别名: 3-ethyl-3-phenyl-4-(1-phenyl-propylidene)-oxetan-2-one；(4Z)-3-ethyl-3-phenyl-4-(1-phenylpropylidene)oxetan-2-one
• CAS: 1114455-09-2
• 化学式: C₂₀H₂₀O₂
• 分子量: 292.378
• InChiKey: QOQUKFUWHACLHC-ZCXUNETKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Z-3-ethyl-3-phenyl-4-(1-phenyl-propylidene)-oxetan-2-one 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 0.83h， 以74%的产率得到3-hydroxymethyl-3,5-diphenyl-heptan-4-one
  参考文献：
  名称：

  Organocatalytic Dimerization of Ketoketenes

  摘要：

  A general method for the catalytic dimerization of ketoketenes is described. Tri-n-butylphosphine was found to be the optimal organocatalyst for the racemic reaction. When lithium iodide was used as an additive, the reaction was rendered selective for dimer formation (dimer/trimer >= 16:1). Ring-opening reactions of the ketoketene dimers as well as preliminary studies toward the development of an asymmetric variant are also reported.

  DOI：

  10.1021/jo8024785
• 作为产物：
  描述：

  2-苯基-1-丁烯-1-酮 在 三丁基膦 、 lithium iodide 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 4.0h， 以84%的产率得到Z-3-ethyl-3-phenyl-4-(1-phenyl-propylidene)-oxetan-2-one
  参考文献：
  名称：

  膦催化酮烯的立体选择性二聚

  摘要：

  讨论了膦催化的乙烯酮均二聚反应优化研究的全部细节，以及不对称变体的详细开发。揭示了对膦催化的烯酮异二聚反应的发展的研究。还提出了对二聚反应可能的反应机理的讨论，并由中间体的光谱分析和捕集实验提供了支持。

  DOI：

  10.1016/j.tet.2020.131838

文献信息

• Mechanistic studies of the phosphine-catalyzed homodimerization of ketoketenes
  作者：Pei-Hsun Wei、Ahmad A. Ibrahim、Mukulesh Mondal、Divya Nalla、Gero D. Harzmann、Frank A. Tedeschi、Kraig A. Wheeler、Nessan J. Kerrigan

  DOI：10.1016/j.tetlet.2010.10.026

  日期：2010.12

  ketoketenes has been explored and compared with that of the previously reported trialkylphosphite-mediated reactions. NMR studies of the PBu3-catalyzed reaction implicated the involvement of tetravalent phosphonium intermediates. Phosphonium intermediates in the catalytic cycle were trapped through reaction with trimethylsilyl chloride and 4-chlorobenzaldehyde, and the resulting products were characterized

  已经探索了PBu 3催化酮酮的均二聚的机理，并将其与先前报道的亚磷酸三烷基酯介导的反应进行了比较。PBu 3的NMR研究-催化的反应牵涉到四价involvement中间体的参与。通过与三甲基甲硅烷基氯和4-氯苯甲醛反应，捕集催化循环中的intermediate中间体，并对所得产物进行了表征。这些研究的结果是开发了一种化学计量生成烯醇化phospho的方法。与三烷基亚磷酸酯介导的二甲基乙烯酮均二聚机理相反，没有证据表明五价膦烷中间体参与三烷基膦催化的酮乙烯均二聚反应。甲基苯基烯酮二聚体的X射线晶体结构分析表明，其具有关于环外烯烃的Z-几何形状。
• Regioselective synthesis of highly substituted enol esters from ketoketene dimer β-lactones
  作者：Eric C Salo、Kyle R Dayak、Jacob Huxford、Pei-Hsun Wei、Nicholas J Peraino、Nessan Joseph Kerrigan

  DOI：10.3998/ark.5550190.p008.443

  日期：——

  A method for the regioselective synthesis of highly substituted enol esters from ketoketene dimers β-lactones is described. Methylphenylketene dimer was subjected to a sequential one-pot reaction sequence involving ring-opening with an organolithium to give an enolate intermediate, followed by enolate acylation with an acyl chloride to give a highly substituted enol ester as the final product. Complete

  描述了一种从酮酮二聚体 β-内酯区域选择性合成高度取代的烯醇酯的方法。甲基苯基乙烯酮二聚体经历一个连续的一锅反应序列，包括用有机锂开环得到烯醇中间体，然后用酰氯烯醇酰化得到高度取代的烯醇酯作为最终产物。在所有情况下都观察到烯醇的 O-酰化的完全区域选择性。酮烯二聚体向高度取代的烯醇酯的一锅法转化率高达 70%。
• Synthesis of 1,3-diketones through ring-opening of ketoketene dimer β-lactones
  作者：Ahmad A. Ibrahim、Stephen M. Smith、Sarah Henson、Nessan J. Kerrigan

  DOI：10.1016/j.tetlet.2009.09.158

  日期：2009.12

  The reaction of ketoketene dimers with organolithium reagents afforded 1,3-diketones in good to excellent yields, and with good diastereoselectivity in some cases.

  酮丁烯二聚体与有机锂试剂的反应可提供1,3-二酮，收率好至极好，在某些情况下具有良好的非对映选择性。
• Phosphine-catalyzed stereoselective dimerizations of ketenes
  作者：Ahmad A. Ibrahim、Pei-Hsun Wei、Gero D. Harzmann、Divya Nalla、Mukulesh Mondal、Kraig A. Wheeler、Nessan J. Kerrigan

  DOI：10.1016/j.tet.2020.131838

  日期：2021.1

  Full details of optimisation studies of the phosphine-catalyzed ketene homodimerization reaction and the detailed development of an asymmetric variant are discussed. Studies towards the development of a phosphine-catalyzed ketene heterodimerization reaction are revealed. A discussion of possible reaction mechanisms for the dimerization reactions, supported by spectroscopic analysis of intermediates

  讨论了膦催化的乙烯酮均二聚反应优化研究的全部细节，以及不对称变体的详细开发。揭示了对膦催化的烯酮异二聚反应的发展的研究。还提出了对二聚反应可能的反应机理的讨论，并由中间体的光谱分析和捕集实验提供了支持。
• Organocatalytic Dimerization of Ketoketenes
  作者：Ahmad A. Ibrahim、Gero D. Harzmann、Nessan J. Kerrigan

  DOI：10.1021/jo8024785

  日期：2009.2.20

  A general method for the catalytic dimerization of ketoketenes is described. Tri-n-butylphosphine was found to be the optimal organocatalyst for the racemic reaction. When lithium iodide was used as an additive, the reaction was rendered selective for dimer formation (dimer/trimer >= 16:1). Ring-opening reactions of the ketoketene dimers as well as preliminary studies toward the development of an asymmetric variant are also reported.