5-oxo-6-phenyl-3,3a,4,5-tetrahydro-1H-pentalene-2,2-dicarboxylic acid diethyl ester | 143668-01-3

• 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: 5-oxo-6-phenyl-3,3a,4,5-tetrahydro-1H-pentalene-2,2-dicarboxylic acid diethyl ester
• 英文别名: (+/-)-diethyl 2-phenyl-3-oxobicyclo<3.3.0>oct-1-ene-7,7-dicarboxylate；diethyl 5-oxo-6-phenyl-3,3a,4,5-tetrahydropentalene-2,2(1H)-dicarboxylate；diethyl 7-oxo-8-phenyl-bicyclo[3.3.0]oct-1(8)-ene-3,3-dicarboxylate；diethyl 5-oxo-6-phenyl-1,3,3a,4-tetrahydropentalene-2,2-dicarboxylate
• CAS: 143668-01-3
• 化学式: C₂₀H₂₂O₅
• 分子量: 342.392
• InChiKey: RGGFNIPHJDEXKG-UHFFFAOYSA-N

物化性质

• 沸点：
  467.0±45.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  diethyl 2-allyl-2-(3-(trimethylsilyl)prop-2-yn-1-yl)malonate 在 palladium on activated charcoal 一氯化碘 、 sodium carbonate 作用下， 以 乙二醇二甲醚 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 12.0h， 生成 5-oxo-6-phenyl-3,3a,4,5-tetrahydro-1H-pentalene-2,2-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Practical and Efficient Suzuki−Miyaura Cross-Coupling of 2-Iodocycloenones with Arylboronic Acids Catalyzed by Recyclable Pd(0)/C

  摘要：

  The first Suzuki-Miyaura cross-coupling of 2-iodocycloenones with arylboronic acids catalyzed by 10% Pd(O)/C is described as an interesting alternative to classical homogeneous conditions. Most of the substrate reacted under mild condition at 25 degrees C under air in aqueous DME. The conditions described tolerate a wide range of iodoenones and boronic acids. Notably, the procedure features inexpensive reagents and solvents with low toxicity rendering the method environmentally benign. Additionally 10% Pd(O)/C could be recovered and efficiently reused at least five times without significant alteration of the yields of the cross-coupled product.

  DOI：

  10.1021/jo051501b

文献信息

• Rhodium(<scp>i</scp>)-catalyzed Pauson–Khand-type reaction using formic acid as a CO surrogate: an alternative approach for indirect CO₂ utilization
  作者：Xian-Dong Lang、Fei You、Xing He、Yi-Chen Yu、Liang-Nian He

  DOI：10.1039/c8gc03933j

  日期：——

  (PK-type) reaction of various substituted 1,6-enynes to afford bicyclic cyclopentenones in moderate to good yields. High TON value of up to 263 and good results in the gram-scale experiment were also obtained, demonstrating the efficacy of this methodology. In addition, heterocyclic molecules of pharmaceutical importance were also furnished via inter- or intra-molecular hetero-PK-type reactions, further

  已发现甲酸是各种取代的1，6-炔烃进行铑（I）催化的Pauson-Khand型（PK型）反应的理想CO替代物，以中等至良好的产率提供双环环戊烯酮。还获得了高达263的高TON值，并且在克级实验中也获得了良好的结果，证明了该方法的有效性。另外，还通过分子间或分子内的异PK型反应提供了具有药学重要性的杂环分子，从而进一步拓宽了当前策略的应用范围。在该协议中，甲酸是作为桥接分子用于将CO 2转化为CO，因为甲酸是通过CO 2的催化加氢制备的并在乙酸酐存在下容易释放出CO。因此，该方法代表了一种绿色，间接的方法，可用于制备增值化合物时对CO 2进行化学增值。
• CO-Transfer Carbonylation Reactions. A Catalytic Pauson−Khand-Type Reaction of Enynes with Aldehydes as a Source of Carbon Monoxide
  作者：Tsumoru Morimoto、Koji Fuji、Ken Tsutsumi、Kiyomi Kakiuchi

  DOI：10.1021/ja0126881

  日期：2002.4.1

  The reaction of enynes with aldehydes in the presence of a catalytic amount of [RhCl(cod)](2)/dppp results in the Pauson-Khand-type reaction without the use of gaseous carbon monoxide to give bicyclic cyclopentenones in high yields (14 examples). Aldehydes serve as a source of carbon monoxide, and their carbonyl moiety is transferred to enynes, resulting in the formation of the carbonylated products

  在催化量的 [RhCl(cod)](2)/dppp 存在下，烯炔与醛的反应会导致 Pauson-Khand 型反应，而无需使用气态一氧化碳，以高产率得到双环环戊烯酮 (14例子）。醛作为一氧化碳的来源，它们的羰基部分被转移到烯炔，导致形成羰基化产物。该反应代表了 CO 转移羰基化的第一个例子。
• Rhodium-Catalyzed Pauson-Khand-Type Reaction Using Alcohol as a Source of Carbon Monoxide
  作者：Ji Hoon Park、Yoonhee Cho、Young Keun Chung

  DOI：10.1002/anie.201001246

  日期：2010.7.12

  cyclopentenones have been synthesized from enynes in alcohol in the presence of a rhodium catalyst through a newly developed auto‐tandem catalytic reaction. This process combines three mechanistically distinctive reactions—an oxidation of alcohols, a decarbonylation of aldehydes, and a carbonylative [2+2+1] cycloaddition (see scheme; dppp=propane‐l,3‐diylbis(diphenylphosphane)).

  三合一锅！双环环戊烯酮是在铑催化剂存在下，通过新开发的自动串联催化反应，由炔烃在醇中合成的。此过程结合了三个机械上独特的反应-醇的氧化，醛的脱羰基和羰基化的[2 + 2 + 1]环加成反应（请参见方案； dppp =丙烷-1,3-二联双（二苯基膦））。
• Cobalt Carbonyl-Mediated Carbocyclizations of Enynes:  Generation of Bicyclooctanones or Monocyclic Alkenes
  作者：Marie E. Krafft、Llorente Vicente R. Boñaga、James A. Wright、Chitaru Hirosawa

  DOI：10.1021/jo016118v

  日期：2002.2.1

  Depending on the thermolytic conditions, dicobalthexacarbonyl-complexed enynes underwent cyclizations to provide different carbocyclic frameworks. Bicyclopentanones were formed from enyne-Co2(CO)6 complexes, or from enynes that were treated with Co2(CO)8, or more effectively, with Co4(CO)12 in an alcoholic solvent under a H2 or N2 atmosphere. This transformation proceeded via a sequential cyclocarbonylation

  取决于热解条件，二钴六羰基复合的烯炔进行环化以提供不同的碳环骨架。双环戊酮是由烯炔-Co2（CO）6配合物形成的，或者由在乙醇溶剂中在H2或N2气氛下用Co2（CO）8或更有效地用Co4（CO）12处理的烯炔形成。该转化通过顺序的环羰基化和1，4-还原进行，并且是使用羰基钴簇的第一个解释。在这些条件下，大概生成了氢化钴，其介导了烯酮还原为饱和酮。相反，在双氢戊烯酮产物之外，在氢气气氛下在甲苯中二巴杂六羰基络合物的炔炔的热解导致它们的还原环化以中等收率形成单环烯烃。在某些情况下，向反应中加入氢硅烷会完全抑制双环戊烯酮的形成。前者的结果证明了在环加成反应之后发生的反应，而后者描述了在Pauson-Khand反应途径中正常途径中断的另一个例子。
• Scope of the Intramolecular Titanocene-Catalyzed Pauson−Khand Type Reaction¹
  作者：Frederick A. Hicks、Natasha M. Kablaoui、Stephen L. Buchwald

  DOI：10.1021/ja990682u

  日期：1999.6.1

  A Pauson−Khand type conversion of enynes to bicyclic cyclopentenones employing the commercially available precatalyst titanocene dicarbonyl is described. This methodology shows excellent functional group tolerance for a group 4 metallocene-catalyzed process. The scope and limitations of this cyclization with respect to 1,6-, 1,7- and 1,8-enynes with a variety of terminal alkyne substituents, chiral

  描述了使用市售的前催化剂二茂钛二羰基将烯炔转化为双环环戊烯酮的 Pauson-Khand 型转化。该方法对第 4 族茂金属催化过程显示出优异的官能团耐受性。详细描述了关于具有各种末端炔烃取代基的 1,6-、1,7- 和 1,8- 烯炔、手性烯炔和含有取代烯烃的烯炔的这种环化的范围和限制。已经提出了涉及中间体钛环戊烯羰基化的机制。