2-(1-Methyl-3-oxo-propyl)-malonic acid diisopropyl ester | 532434-56-3

• 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-(1-Methyl-3-oxo-propyl)-malonic acid diisopropyl ester
• 英文别名: Dipropan-2-yl 2-(4-oxobutan-2-yl)propanedioate；dipropan-2-yl 2-(4-oxobutan-2-yl)propanedioate
• CAS: 532434-56-3
• 化学式: C₁₃H₂₂O₅
• 分子量: 258.315
• InChiKey: ACXJJJAMDVXLCX-UHFFFAOYSA-N

物化性质

• 沸点：
  334.0±32.0 °C(Predicted)
• 密度：
  1.037±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 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：

  2-(1-Methyl-3-oxo-propyl)-malonic acid diisopropyl ester 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 diisopropyl (S)-(+)-(1-methyl-3-oxohexyl)malonate
  参考文献：
  名称：

  Asymmetric Michael Addition of Malonate Anions to Prochiral Acceptors Catalyzed by l-Proline Rubidium Salt

  摘要：

  L-Proline rubidium salt catalyzes the asymmetric Michael addition of malonate anions to prochiral enones and enals. This method can be applied to a wide range of substrates to give adducts with a predictable absolute configuration: (S)-adducts from (E)-enones/enals and (R)-adducts from cyclic (Z)-enones. Both the secondary amine moiety and the carboxylate moiety are critical for the catalytic activity and asymmetric induction. Varying the countercation also affects the reaction course. High enantiomeric excesses were attained when di(tert-butyl) malonate was added to (E)-enones in the presence of CsF. The stereochemistry of the Michael reaction indicates that asymmetric induction takes place via enantioface discrimination involving the acceptor alpha-carbon atom rather than the beta-carbon atom.

  DOI：

  10.1021/jo960216c
• 作为产物：
  描述：

  巴豆醛 、 丙二酸二异丙酯 在 lithium aluminium tetrahydride 、 (S)-C₁₃H₁₉NO₃ 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以70%的产率得到2-(1-Methyl-3-oxo-propyl)-malonic acid diisopropyl ester
  参考文献：
  名称：

  Novel heterobimetallic catalysts for asymmetric Michael reactions

  摘要：

  The newly developed chiral catalysts 1 and 2 show opposite enantioselectivity in Michael addition reactions of cyclic enones and malonates resulting in the production of both enantiomers of products in good chemical yield and enantiomeric excess. Al-27 NMR studies showed the formation of different types of complexes for catalysts 1 and 2 and the enantioselectivity was found to be dependent on the nature of the aluminium complex formed. Scope of the reaction was extended to other Michael donors such as nitro alkanes and thiols. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00737-1

文献信息

• Novel heterobimetallic catalysts for asymmetric Michael reactions
  作者：S Velmathi、S Swarnalakshmi、S Narasimhan

  DOI：10.1016/s0957-4166(02)00737-1

  日期：2003.1

  The newly developed chiral catalysts 1 and 2 show opposite enantioselectivity in Michael addition reactions of cyclic enones and malonates resulting in the production of both enantiomers of products in good chemical yield and enantiomeric excess. Al-27 NMR studies showed the formation of different types of complexes for catalysts 1 and 2 and the enantioselectivity was found to be dependent on the nature of the aluminium complex formed. Scope of the reaction was extended to other Michael donors such as nitro alkanes and thiols. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Asymmetric Michael Addition of Malonate Anions to Prochiral Acceptors Catalyzed by <scp>l</scp>-Proline Rubidium Salt
  作者：Masahiko Yamaguchi、Tai Shiraishi、Masahiro Hirama

  DOI：10.1021/jo960216c

  日期：1996.1.1

  L-Proline rubidium salt catalyzes the asymmetric Michael addition of malonate anions to prochiral enones and enals. This method can be applied to a wide range of substrates to give adducts with a predictable absolute configuration: (S)-adducts from (E)-enones/enals and (R)-adducts from cyclic (Z)-enones. Both the secondary amine moiety and the carboxylate moiety are critical for the catalytic activity and asymmetric induction. Varying the countercation also affects the reaction course. High enantiomeric excesses were attained when di(tert-butyl) malonate was added to (E)-enones in the presence of CsF. The stereochemistry of the Michael reaction indicates that asymmetric induction takes place via enantioface discrimination involving the acceptor alpha-carbon atom rather than the beta-carbon atom.