2-((E)-4-Oxo-but-2-enyl)-2-prop-2-ynyl-malonic acid dimethyl ester | 120545-12-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-((E)-4-Oxo-but-2-enyl)-2-prop-2-ynyl-malonic acid dimethyl ester
• 英文别名: dimethyl 2-[(E)-4-oxobut-2-enyl]-2-prop-2-ynylpropanedioate
• CAS: 120545-12-2
• 化学式: C₁₂H₁₄O₅
• 分子量: 238.24
• InChiKey: JUNLQKSTUALDHH-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.49
• 重原子数：
  17.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  69.67
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  2-((E)-4-Oxo-but-2-enyl)-2-prop-2-ynyl-malonic acid dimethyl ester 在 Pd₂(dibenzylideneacetone)2*CHCl₃ 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 97.5h， 生成 dimethyl (1R,3aS,4R,8bR)-1-methyl-3-oxo-4-(phenylcarbamoyl)-3a,4,5,6,8,8b-hexahydro-1H-cyclopenta[e][2]benzofuran-7,7-dicarboxylate
  参考文献：
  名称：

  Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System

  摘要：

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.

  DOI：

  10.1021/ja00089a016
• 作为产物：
  描述：

  炔丙基丙二酸二甲酯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 三苯基膦 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 2-((E)-4-Oxo-but-2-enyl)-2-prop-2-ynyl-malonic acid dimethyl ester
  参考文献：
  名称：

  Hydroxy group as a regio- and stereochemical control element for sequential metal-catalyzed and thermal cyclizations

  摘要：

  DOI：

  10.1021/jo00271a006

文献信息

• Rhodium-Catalyzed Intra- and Intermolecular [5 + 2] Cycloaddition of 3-Acyloxy-1,4-enyne and Alkyne with Concomitant 1,2-Acyloxy Migration
  作者：Xing-Zhong Shu、Xiaoxun Li、Dongxu Shu、Suyu Huang、Casi M. Schienebeck、Xin Zhou、Patrick J. Robichaux、Weiping Tang

  DOI：10.1021/ja2109097

  日期：2012.3.21

  type of rhodium-catalyzed [5 + 2] cycloaddition was developed for the synthesis of seven-membered rings with diverse functionalities. The ring formation was accompanied by a 1,2-acyloxy migration event. The five- and two-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes (ACEs) and alkynes, respectively. Cationic rhodium(I) catalysts worked most efficiently for the intramolecular cycloaddition

  开发了一种新型的铑催化 [5 + 2] 环加成反应，用于合成具有多种功能的七元环。环的形成伴随着 1,2-酰氧基迁移事件。环加成的五碳和二碳组分分别是 3-酰氧基-1,4-烯炔 (ACE) 和炔烃。阳离子铑（I）催化剂对分子内环加成最有效，而只有中性铑（I）配合物才能促进分子间反应。在这两种情况下，缺电子的亚磷酸酯或膦配体通常可以提高环加成的效率。在分子内和分子间反应中研究了 ACE 和炔烃的范围。由此产生的七元环产物具有三个可以选择性功能化的双键。
• Transfer of Chirality in the Rhodium-Catalyzed Intramolecular [5+2] Cycloaddition of 3-Acyloxy-1,4-enynes (ACEs) and Alkynes: Synthesis of Enantioenriched Bicyclo[5.3.0]decatrienes
  作者：Xing-zhong Shu、Casi M. Schienebeck、Wangze Song、Ilia A. Guzei、Weiping Tang

  DOI：10.1002/anie.201306919

  日期：2013.12.16

  Chiral bicycles: Enantioenriched bicyclo[5.3.0]decatrienes were prepared from readily available chiral 3‐acyloxy‐1,4‐enynes (ACEs) for the first time. In most cases, the chirality of the ACEs could be transferred to the bicyclic products with high efficiency. Inversion of the configuration was observed, thus confirming the predictions of previous computational studies.

  手性自行车：首次从现成的手性 3-酰氧基-1,4-烯炔 (ACE) 制备对映体富集的双环 [5.3.0] 癸三烯。在大多数情况下，ACE 的手性可以高效地转移到双环产品中。观察到配置的反转，从而证实了先前计算研究的预测。
• TROST, BARRY M.;LEE, DONNA C., J. ORG. CHEM., 54,(1989) N0, C. 2271-2274
  作者：TROST, BARRY M.、LEE, DONNA C.

  DOI：——

  日期：——