trans-2,5-dimethyl-3,4-diphenyl-2-cyclopenten-1-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: trans-2,5-dimethyl-3,4-diphenyl-2-cyclopenten-1-one
• 英文别名: trans-2,5-dimethyl-3,4-diphenylcyclopent-2-en-1-one；2,5-dimethyl-3,4-diphenylcyclopent-2-enone；(+/-)-2,5t-dimethyl-3,4r-diphenyl-cyclopent-2-enone；(+/-)-2,5t-Dimethyl-3,4r-diphenyl-cyclopent-2-enon；(4R,5S)-2,5-dimethyl-3,4-diphenylcyclopent-2-en-1-one
• 化学式: C₁₉H₁₈O
• 分子量: 262.351
• InChiKey: FPMNYEMWMGKIKG-SUMWQHHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 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：

  trans-2,5-dimethyl-3,4-diphenyl-2-cyclopenten-1-one 、 甲基锂 以 四氢呋喃 、 乙醚 为溶剂， 以23%的产率得到1,2,3-trimethyl-4,5-diphenyl-cyclopentadiene
  参考文献：
  名称：

  Direct synthesis of polysubstituted cyclopentenones from ketones and aldehydes catalyzed by zirconium compounds

  摘要：

  DOI：

  10.1021/jo00068a060
• 作为产物：
  描述：

  4-hydroxy-2,5-dimethyl-3,4-diphenylcyclopent-2-enone 在 磷化氢 、 次碘(I)酸 、 溶剂黄146 作用下， 生成 trans-2,5-dimethyl-3,4-diphenyl-2-cyclopenten-1-one
  参考文献：
  名称：

  Some Cyclopentenones and Supposed Cyclopentenones

  摘要：

  DOI：

  10.1021/ja01534a050

文献信息

• Synthesis of oxathiane and morpholine from acyclic precursors: a modified Mitsunobu reaction
  作者：Nidhin Paul、Selvam Kaladevi、Arockiam Jesin Beneto、Shanmugam Muthusubramanian、Nattamai Bhuvanesh

  DOI：10.1016/j.tet.2012.06.029

  日期：2012.8

  Synthesis of a set of isomeric 2,4,6-triarylmorpholines and 2,6-diaryloxathianes from the corresponding 1,5-diols has been described. The method provides an efficient route to six-membered heterocycles from acyclic diols and is found to be better than Mitsunobu procedure in yield and waste management. In a related study, the ring contraction of pyranone to two isomeric cyclopentenone derivatives through

  已经描述了由相应的1，5-二醇合成一组异构的2，4，6-三芳基吗啉和2，6-二芳基氧杂蒽。该方法提供了从无环二醇到六元杂环的有效途径，发现在产率和废物管理方面比Mitsunobu方法更好。在相关研究中，已经注意到通过纳扎罗夫反应将吡喃酮环收缩成两个异构的环戊烯酮衍生物。
• Natural deep eutectic solvents as an efficient and reusable active system for the Nazarov cyclization
  作者：Stefano Nejrotti、Marta Iannicelli、Salwa Simona Jamil、Davide Arnodo、Marco Blangetti、Cristina Prandi

  DOI：10.1039/c9gc03465j

  日期：——

  Natural deep eutectic solvents have emerged as alternative non-toxic, non-aqueous solvents for an increasing number of synthetic transformations. Remarkably, in some cases one (or more) components of the NaDES plays an active role in the reaction mechanism and directly participates as either a catalyst or a reagent in the reaction. In this paper, we tested several NaDESs in which one of the components

  天然的深共熔溶剂已成为替代的无毒，无水溶剂，可用于越来越多的合成转化中。值得注意的是，在某些情况下，NaDES的一种（或多种）组分在反应机理中起积极作用，并直接作为催化剂或试剂参与反应。在本文中，我们测试了几种NaDES，其中的一种组分是羧酸作为介质，以进行二乙烯基酮的Nazarov环化反应，获得环戊烯酮，这是天然化合物中普遍存在的基序。优化了反应条件，研究了C-，O-和N的范围。衍生的化合物。为了评估所提出方法的完全可持续性，对工艺的可回收性和可扩展性进行了研究，从而证明在完全回收介质的情况下，可以进行多克制剂的制备。
• Optimization of Nazarov Cyclization of 2,4-Dimethyl-1,5-diphenylpenta-1,4-dien-3-one in Deep Eutectic Solvents by a Design of Experiments Approach
  作者：Stefano Nejrotti、Alberto Mannu、Marco Blangetti、Salvatore Baldino、Andrea Fin、Cristina Prandi

  DOI：10.3390/molecules25235726

  日期：——

  using phosphonium-based Deep Eutectic Solvents as sustainable non-innocent reaction media is described. A two-level full factorial Design of Experiments was conducted for elucidating the effect of the components of the eutectic mixture and optimizing the reaction conditions in terms of temperature, time, and substrate concentration. In the presence of the Deep Eutectic Solvent (DES) triphenylmethylphosphonium

  描述了使用基于鏻的深共晶溶剂作为可持续的非无害反应介质对模型二乙烯基酮进行前所未有的 Nazarov 环化。进行了两水平全因子实验设计，以阐明共晶混合物组分的影响，并在温度、时间和底物浓度方面优化反应条件。在深共晶溶剂 (DES) 三苯基甲基溴化鏻/乙二醇的存在下，可以转化超过 80% 的 2,4-二甲基-1,5-二苯基五-1,4-二烯-3-酮，以特定的转化率转化为 62% 的环戊烯酮 Nazarov 衍生物（16 小时，60 °C）。对于在 DES 三苯基甲基溴化鏻/乙酸中进行的反应，即使在 25 °C 下，Nazarov 产物的百分比也超过 95%，从而获得了定量转化。优化数据的表面响应分析提供了一个有用的工具来确定导致起始材料定量转化的最佳操作条件，完全抑制不需要的副反应、高产率和选择性。优化后，可以将超过 90% 的模型底物转化为所需的环戊烯酮，顺式百分比高达 77%。实施模型的实
• Interrupting Nazarov Reaction with Different Trapping Modality: Utilizing Potassium Alkynyltrifluoroborate as a σ-Nucleophile
  作者：Ronny William、Siming Wang、Asadulla Mallick、Xue-Wei Liu

  DOI：10.1021/acs.orglett.6b01606

  日期：2016.9.16

  cation intermediate generated following Nazarov cyclization of dienone has been successfully intercepted with potassium alkynyltrifluoroborates which act as σ-nucleophiles in the presence of BF3·Et2O. This new trapping modality allowed unprecedented introduction of an alkynyl moiety to the cyclopentanone framework by means of an interrupted Nazarov reaction. The α-alkynyl cyclopentanone product can

  Nazarov环化二烯酮后生成的假定的羟烯丙基阳离子中间体已成功被存在BF 3 ·Et 2 O的σ-亲核试剂炔基三氟硼酸钾拦截。这种新的捕集方式允许将炔基部分空前引入环戊酮框架通过中断的纳扎罗夫反应。可以将α-炔基环戊酮产物进一步转化为一系列高密度官能化的环状化合物。
• 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.