丁酰丙二酸二乙酯 | 4761-26-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 丁酰丙二酸二乙酯
• 英文名称: ethyl 2-carbethoxy-5-oxocaproate
• 英文别名: diethyl 2-(3-oxobutyl)malonate；diethyl (3'-oxobutyl)malonate；ethyl 2-ethoxycarbonyl-5-oxohexanoate；Diethyl (3-oxobutyl)malonate；diethyl 2-(3-oxobutyl)propanedioate
• CAS: 4761-26-6
• 化学式: C₁₁H₁₈O₅
• 分子量: 230.261
• InChiKey: ALUWYSWCNMTCSN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  16
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  丁酰丙二酸二乙酯 在 乙醇 、 sodium ethanolate 作用下， 生成 1,3-环己二酮
  参考文献：
  名称：

  Mannich; Fourneau, Chemische Berichte, 1938, vol. 71, p. 2090

  摘要：

  DOI：
• 作为产物：
  描述：

  4-oxo-pentane-1,1,3-tricarboxylic acid triethyl ester 在 盐酸 、 乙醇 作用下， 生成 丁酰丙二酸二乙酯
  参考文献：
  名称：

  Nakazawa; Matsuura, Yakugaku Zasshi/Journal of the Pharmaceutical Society of Japan, 1951, vol. 71, p. 178,180

  摘要：

  DOI：

文献信息

• Nitrogen Fixation: Synthesis of Heterocycles Using Molecular Nitrogen as a Nitrogen Source
  作者：Miwako Mori、Masaya Akashi、Masanori Hori、Katsutoshi Hori、Mayumi Nishida、Yoshihiro Sato

  DOI：10.1246/bcsj.77.1655

  日期：2004.9

  Nitrogen fixation using transition metals is a fascinating process. We have already reported on the incorporation of molecular nitrogen into organic compounds using a titanium–nitrogen complex reported by Yamamoto. We developed a novel titanium-catalyzed nitrogenation procedure using TiCl4 in the presence of an excess amount of Li and TMSCl. In this reaction, a 1 atm pressure of nitrogen gas can be used and the reaction proceeds at room temperature. The procedure is very simple. A THF solution of TiCl4 or Ti(OiPr)4 (1 equiv.), Li (10 equiv.), and TMSCl (10 equiv.) was stirred under an atmosphere of nitrogen at room temperature overnight to give titanium–nitrogen complexes. Although the structures of the titanium–nitrogen complexes have not yet been determined, they would consist of N(TMS)3, X2TiN(TMS)2, and XTi=NTMS. Using this procedure, various heterocycles, such as indole, quinoline, pyrrole, pyrrolizine, and indolizine derivatives, could be synthesized from molecular nitrogen in good-to-moderate yields as a stoichiometric reaction based on a titanium complex by a one-pot reaction. Furthermore, monomorine I and pumiliotoxin C were synthesized from molecular nitrogen as a nitrogen source. This procedure was further extended for the syntheses of heterocycles using a catalytic amount of titanium complex; also, indole and pyrrole derivatives were obtained in high yields.

  过渡金属固氮是一个迷人的过程。我们之前已经报道过使用Yamamoto报道的钛-氮配合物将分子氮引入有机化合物的方法。我们开发了一种新的钛催化氮化过程，使用TiCl4在过量Li和TMSCl的存在下进行。在这种反应中，可以使用1大气压的氮气，反应在室温下进行。这个过程非常简单。将TiCl4或Ti(OiPr)4（1 equiv.）、Li（10 equiv.）和TMSCl（10 equiv.）的THF溶液在氮气气氛下在室温下搅拌过夜，得到钛-氮配合物。尽管钛-氮配合物的结构尚未确定，但它们可能由N(TMS)3、X2TiN(TMS)2和XTi=NTMS组成。使用这种方法，可以通过钛配合物作为定量反应的单锅反应，以良好至中等的收率合成各种杂环化合物，如吲哚、喹啉、吡咯、吡咯啉和吲哚啉衍生物。此外，使用分子氮作为氮源合成了monomorine I和pumiliotoxin C。这种方法进一步扩展，用于使用催化量的钛配合物合成杂环化合物；此外，以高收率获得了吲哚和吡咯衍生物。
• Nickel-Catalyzed Benzylic Substitution of Benzyl Esters with Malonates as a Soft Carbon Nucleophile
  作者：Hiroaki Tsuji、Keisuke Hashimoto、Motoi Kawatsura

  DOI：10.1021/acs.orglett.9b03475

  日期：2019.11.1

  The nickel-catalyzed benzylic substitution of benzyl alcohol derivatives with a soft carbon nucleophile is extremely rare compared to that with a hard carbon nucleophile. We have achieved the nickel-catalyzed benzylic substitution of benzyl esters with malonates as a soft carbon nucleophile. Primary and secondary benzyl 2,3,4,5,6-pentafluorobenzoates as well as a wide variety of malonate derivatives

  与用硬碳亲核试剂相比，用软碳亲核试剂对苯甲醇衍生物进行镍催化的苄基取代极为罕见。我们已经实现了丙二酸酯作为软碳亲核试剂的镍催化苄基酯的苄基取代。2,3,4,5,6-五氟苯甲酸苄酯和仲苄酯以及各种丙二酸酯衍生物在镍催化的反应中具有良好的耐受性，以46-86％的收率提供了相应的烷基化产物（34个实例）。此外，我们提出了一种可能的反应机理，将经由η经历1 -和η 3个-benzylnickel中间体。
• Neutral Lewis Bases as Activators of Molecular Sieves in the Conjugate Addition of 1,3-Dicarbonyl Compounds
  作者：Arrigo Scettri、Rosaria Villano

  DOI：10.1055/s-2005-861810

  日期：——

  The catalytic properties of 3 A molecular sieves in the promotion of Michael addition of 1,3-dicarbonyl compounds are significantly improved by activation with several neutral Lewis bases. Comparable efficiency can be observed under solvent-free conditions.

  3 A分子筛在促进1,3-二羰基化合物迈克尔加成中的催化性能通过几种中性路易斯碱的活化得到显着改善。在无溶剂条件下可以观察到相当的效率。
• Surface-mediated solid phase michael reaction: dramatic acceleration on alumina
  作者：Brindaban C. Ranu、Sanjay Bhar、Dipak C. Sarkar

  DOI：10.1016/0040-4039(91)85093-k

  日期：1991.6

  The Michael reaction of several β-dicarbonyl compounds, ethyl cyanoacetate, and diethyl malonate as donors with methyl vinyl ketone, acrolein and methyl acrylate as acceptors are carried out very efficiently on Al2O3 surface without any solvent.

  几种β-二羰基化合物，氰基乙酸乙酯和丙二酸二乙酯（作为供体）与甲基乙烯基酮，丙烯醛和丙烯酸甲酯作为受体的迈克尔反应非常有效地在Al 2 O 3表面上进行，而无需任何溶剂。
• Ruthenium-catalyzed stereospecific benzylic alkylation of optically active benzyl esters with malonate nucleophiles
  作者：Hiroaki Tsuji、Koki Suzuki、Motoi Kawatsura

  DOI：10.1016/j.tetlet.2021.152947

  日期：2021.4

  The transition metal-catalyzed stereospecific benzylic alkylation of optically active benzyl esters with active methylene compounds remains extremely rare. Herein, we describe the study for the ruthenium-catalyzed benzylic alkylation of chiral benzyl esters with malonates as a carbon nucleophile. A combination of [Cp*RuCl2]2 and picolinic acid found to be effective for the title reaction, providing

  旋光性苄基酯与活性亚甲基化合物的过渡金属催化的立体有择性苄基烷基化仍然极为罕见。在这里，我们描述了手性苄酯与丙二酸酯作为碳亲核试剂的钌催化苄烷基化的研究。发现[Cp * RuCl 2 ] 2和吡啶甲酸的组合对于标题反应是有效的，提供手性苄基烷基化产物，并且保留了起始原料的立体化学。我们提出钌催化将通过双重转化机制进行。

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