2-cyano-2-methyl-5-oxopentanoic acid ethyl ester | 121730-73-2

• 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-cyano-2-methyl-5-oxopentanoic acid ethyl ester
• 英文别名: ethyl 2-cyano-4-formyl-2-methylbutanoate；ethyl 2-cyano-2-methyl-5-oxopentanoate
• CAS: 121730-73-2
• 化学式: C₉H₁₃NO₃
• 分子量: 183.207
• InChiKey: QQVPZMFEIHMENS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  13
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  67.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-氰基丙酸乙酯 在 二(氰基苯)二氯化钯 、 silver(I) nitrite 、 copper(II) choride dihydrate 、 氧气 、 sodium hydride 作用下， 以 硝基甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 、 叔丁醇 、 苯 为溶剂， 反应 19.33h， 生成 2-cyano-2-methyl-5-oxopentanoic acid ethyl ester
  参考文献：
  名称：

  通过醛选择性瓦克型氧化实现受阻末端烯烃的催化反马尔科夫尼科夫转化

  摘要：

  报道了一种空间位阻末端烯烃功能化的新策略。在烯丙基或同烯丙基位置带有季碳的烯烃很容易被钯/铜/亚硝酸盐催化氧化成相应的醛。在反应条件下可以耐受多种官能团，包括酯、腈、甲硅烷基醚、乙烯基酯、酮、内酯和 β-酮酯。粗醛产物可以进一步转化，使受阻末端烯烃直接转化为各种其他合成有用的官能团，导致正式的反马尔科夫尼科夫加氢胺化等转化。

  DOI：

  10.1021/jacs.6b08788

文献信息

• 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
• Murahashi, Shun-Ichi; Take, Kazuhiko; Naota, Takeshi, Synlett, 2000, # 7, p. 1016 - 1018
  作者：Murahashi, Shun-Ichi、Take, Kazuhiko、Naota, Takeshi、Takaya, Hikaru

  DOI：——

  日期：——
• 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.
• Chirality Control of Tropos Diphenylmethane-Derived Phosphoramidites by Chiral Dienes: Its Application to Asymmetric Michael Addition
  作者：Koichi Mikami、Kazuki Wakabayashi、Kohsuke Aikawa

  DOI：10.3987/com-08-s(f)102

  日期：——

  The Rh complex of tropos diphenylmethane-derived phosphoramidite could be chirally controlled to adopt single chiral conformation upon addition of a chiral diene. In the asymmetric Michael addition of alpha-cyanocarboxylates catalyzed by the Rh complexes, the chiral diene and bisphenylmethane-derived phosphoramidite functioned to attain higher enantioselectivity and catalytic activity via asymmetric activation.