diethyl 4-cyano-2-(ethoxycarbonyl)-3-methylpentanedioate | 121730-78-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl 4-cyano-2-(ethoxycarbonyl)-3-methylpentanedioate
• 英文别名: Triethyl 3-cyano-2-methyl-1,1,3-propanetricarboxylate；triethyl 3-cyano-2-methylpropane-1,1,3-tricarboxylate
• CAS: 121730-78-7
• 化学式: C₁₄H₂₁NO₆
• 分子量: 299.324
• InChiKey: RTORFWRGIWVRSI-UHFFFAOYSA-N

物化性质

• 沸点：
  397.5±42.0 °C(Predicted)
• 密度：
  1.131±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  21
• 可旋转键数：
  11
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  103
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  diethyl 4-cyano-2-(ethoxycarbonyl)-3-methylpentanedioate 在 [RuH2(PPh3)4] 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 diethyl (1S^*,2R^*,3R^*)-5-acetyl-1-cyano-4-hydroxy-2-methyl-4-cyclohexene-1,3-dicarboxylate
  参考文献：
  名称：

  Ruthenium-catalyzed aldol and Michael reactions of nitriles. Carbon-carbon bond formation by .alpha.-C-H activation of nitriles.

  摘要：

  The ruthenium(II)-catalyzed reaction of nitriles with carbonyl compounds proceeds highly efficiently under neutral and mild conditions to give alpha,beta-unsaturated nitriles. Under similar reaction conditions, nitriles react with olefins bearing electron-withdrawing groups to give the corresponding Michael adducts. The efficiency of the reaction is illustrated by the selective additions to alpha,beta-unsaturated aldehydes and acetylenes bearing electron-withdrawing groups, which are difficult to perform using conventional bases. Chemoselective aldol and Michael reactions of nitriles can be performed in the presence of other active methylene compounds. Tandem Michael and Michael-aldol condensations of nitriles 30 can be performed with high diastereoselectivity. These reactions can be rationalized by assuming oxidative addition of ruthenium(0) to the alpha=C-H bond of nitriles and subsequent insertions to carbonyl compounds or olefins. As the key intermediates and active catalysts hydrido(N-bonded enolato)ruthenium(II) complexes, mer-RuH(NCCHCO(2)R)(NCCH(2)CO(2)R)(PPh(3))(3) (R = Me (41a), Et (41b), n-Bu (41c) have been upon treatment of RuH2(PPh(3))(4) (3) or RuH(C2H4)(PPh(3))(2)(PPh(2)C(6)H(4)) (4) with alkyl cyanoacetates. Kinetic study of the catalytic aldol reaction of ethyl cyanoacetate with benzaldehyde indicates that the rate-determining step reaction of enolato complex 41 with aldehydes.

  DOI：

  10.1021/ja00155a008

文献信息

• Michael Reaction of Stabilized Carbon Nucleophiles Catalyzed by [RuH₂(PPh₃)₄]
  作者：Enrique Gómez-Bengoa、Juan M. Cuerva、Cristina Mateo、Antonio M. Echavarren

  DOI：10.1021/ja961373w

  日期：1996.1.1

  also observed as side reactions. Catalysis by other ruthenium and rhodium complexes has been examined. Selectivity studies performed with malonate and disulfone donors indicate that the catalyst selectively activates Michael donors that can coordinate with ruthenium(II). Additionally, it has been shown that the reaction requires the presence of free phosphine. Therefore, the Michael reaction of stabilized

  缺乏氰基的活性亚甲基化合物如丙二酸酯、β-酮酯、1,3-二酮、1,1-二砜、硝基化合物、Meldrum 酸和蒽酮与常见受体的迈克尔反应在乙腈溶液中在 [RuH2 (PPh3)4]作为催化剂。氰基乙酸盐在有机溶剂中比丙二酸盐酸性更强，也是该反应的极好底物。在许多情况下，也观察到由​​ [RuH2(PPh3)4] 催化的分子内羟醛反应作为副反应。已经研究了其他钌和铑配合物的催化作用。对丙二酸和二砜供体进行的选择性研究表明，该催化剂选择性地激活可以与钌 (II) 配位的迈克尔供体。此外，已经表明该反应需要存在游离膦。所以，稳定的烯醇化物的迈克尔反应似乎是钌和膦催化的反应。从实用的角度来看，使用随手准备...
• Ruthenium-catalyzed aldol and Michael reactions of activated nitriles
  作者：Takeshi Naota、Hiroshi Taki、Masahiko Mizuno、Shunichi Murahashi

  DOI：10.1021/ja00197a073

  日期：1989.7

  Catalyse par RuH 2 (PPh 3 ) 4 des reactions de cyanoesters, dinitriles et du benzeneacetonitrile avec des aldehydes, enaldehydes, cetones et enones pour donner les produits d'aldolisation et d'addition de Michael, correspondants

  Catalyze par RuH 2 (PPh 3 ) 4 des reactors de cyanoesters, dinitriles et du benzonitrile avec des aldehydes, enaldehydes, cetones et enones pour donner les produits d'aldolisation et d'addition de Michael, 通讯员
• Ruthenium-catalyzed aldol and Michael reactions of nitriles. Carbon-carbon bond formation by .alpha.-C-H activation of nitriles.
  作者：Shun-Ichi Murahashi、Takeshi Naota、Hiroshi Taki、Masahiko Mizuno、Hikaru Takaya、Sanshiro Komiya、Yuji Mizuho、Naohiko Oyasato、Makiko Hiraoka

  DOI：10.1021/ja00155a008

  日期：1995.12

  The ruthenium(II)-catalyzed reaction of nitriles with carbonyl compounds proceeds highly efficiently under neutral and mild conditions to give alpha,beta-unsaturated nitriles. Under similar reaction conditions, nitriles react with olefins bearing electron-withdrawing groups to give the corresponding Michael adducts. The efficiency of the reaction is illustrated by the selective additions to alpha,beta-unsaturated aldehydes and acetylenes bearing electron-withdrawing groups, which are difficult to perform using conventional bases. Chemoselective aldol and Michael reactions of nitriles can be performed in the presence of other active methylene compounds. Tandem Michael and Michael-aldol condensations of nitriles 30 can be performed with high diastereoselectivity. These reactions can be rationalized by assuming oxidative addition of ruthenium(0) to the alpha=C-H bond of nitriles and subsequent insertions to carbonyl compounds or olefins. As the key intermediates and active catalysts hydrido(N-bonded enolato)ruthenium(II) complexes, mer-RuH(NCCHCO(2)R)(NCCH(2)CO(2)R)(PPh(3))(3) (R = Me (41a), Et (41b), n-Bu (41c) have been upon treatment of RuH2(PPh(3))(4) (3) or RuH(C2H4)(PPh(3))(2)(PPh(2)C(6)H(4)) (4) with alkyl cyanoacetates. Kinetic study of the catalytic aldol reaction of ethyl cyanoacetate with benzaldehyde indicates that the rate-determining step reaction of enolato complex 41 with aldehydes.