(1R)-2-oxo-1-(3-oxobutyl)-N-phenylcyclopentane-1-carboxamide | 1310737-90-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R)-2-oxo-1-(3-oxobutyl)-N-phenylcyclopentane-1-carboxamide
• CAS: 1310737-90-6
• 化学式: C₁₆H₁₉NO₃
• 分子量: 273.332
• InChiKey: LKSMHDKAARUTNZ-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  63.2
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-氧代环戊羧酸乙酯 在 4-二甲氨基吡啶 、 {Pd(H₂O)2[(R_a)-BINAP]}⁽²⁺⁾*2TfO^(1-) 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 21.5h， 生成 (1R)-2-oxo-1-(3-oxobutyl)-N-phenylcyclopentane-1-carboxamide 、 (1R)-2-oxo-1-(3-oxobutyl)-N-phenylcyclopentane-1-carboxamide
  参考文献：
  名称：

  Unique features of chiral palladium enolates derived from β-ketoamide: structure and catalytic asymmetric Michael and fluorination reactions

  摘要：

  We have previously reported enantioselective reactions of 1,3 -diketones and beta-ketoesters with various electrophiles catalyzed by chiral Pd complex, in which chiral Pd enolates play a key role. Here, we present a detailed examination of Pd-catalyzed enantioselective Michael addition and fluorination reactions of beta-ketoamides. beta-Ketoamide showed higher reactivity than 1,3-diketone and beta-ketoester, though its alpha-proton is likely to be least acidic. Pd enolate formation of beta-ketoamide was much faster than that of beta-ketoester. The crystal structures of (R)-BINAP-Pd-diketone and ketoamide complexes were found to be quite distinct. Pd-diketone complex has bidentate square-planar geometry as have been predicted before, whereas Pd-ketoamide complex was greatly distorted, probably due to steric constraints of the amide bond. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.07.002

文献信息

• Origin of the Enantioselectivity in Organocatalytic Michael Additions of β-Ketoamides to α,β-Unsaturated Carbonyls: A Combined Experimental, Spectroscopic and Theoretical Study
  作者：Adrien Quintard、Diana Cheshmedzhieva、Maria del Mar Sanchez Duque、Anouk Gaudel-Siri、Jean-Valère Naubron、Yves Génisson、Jean-Christophe Plaquevent、Xavier Bugaut、Jean Rodriguez、Thierry Constantieux

  DOI：10.1002/chem.201404481

  日期：2015.1.7

  The organocatalytic enantioselective conjugate addition of secondary β‐ketoamides to α,β‐unsaturated carbonyl compounds is reported. Use of bifunctional Takemoto’s thiourea catalyst allows enantiocontrol of the reaction leading either to simple Michael adducts or spirocyclic aminals in up to 99 % ee. The origin of the enantioselectivity has been rationalised based on combined DFT calculations and kinetic

  据报道，β-酮酰胺仲胺向α，β-不饱和羰基化合物的有机催化对映选择性共轭加成反应。使用双功能Takemoto's硫脲催化剂可以对反应进行对映体控制，从而导致简单的Michael加合物或高达99％ee的螺环缩醛 。基于组合的DFT计算和动力学分析，对映选择性的起源已经合理化。这项研究提供了对反应机理的更深入的了解，其中涉及仲酰胺质子的主要作用，并阐明了底物与催化剂之间发生的复杂相互作用。
• A Cooperative Participation of the Amido Group in the Organocatalytic Construction of All-Carbon Quaternary Stereocenters by Michael Addition with β-Ketoamides
  作者：Maria del Mar Sanchez Duque、Olivier Baslé、Nicolas Isambert、Anouk Gaudel-Siri、Yves Génisson、Jean-Christophe Plaquevent、Jean Rodriguez、Thierry Constantieux

  DOI：10.1021/ol200924e

  日期：2011.7.1

  The secondary amido group of a-substituted beta-ketoamides plays a crucial role in the control of the reactivity and spatial arrangement (selectivity) in the organocatalyzed Michael addition to unsaturated carbonyls. This results in an unprecedented activation mode of substrates through H-bonding interactions allowing the construction of enantiomerically enriched functionalized all-carbon quaternary centers and spiroaminals of high synthetic potential.
• Unique features of chiral palladium enolates derived from β-ketoamide: structure and catalytic asymmetric Michael and fluorination reactions
  作者：Kenji Hayamizu、Naoki Terayama、Daisuke Hashizume、Kosuke Dodo、Mikiko Sodeoka

  DOI：10.1016/j.tet.2015.07.002

  日期：2015.9

  We have previously reported enantioselective reactions of 1,3 -diketones and beta-ketoesters with various electrophiles catalyzed by chiral Pd complex, in which chiral Pd enolates play a key role. Here, we present a detailed examination of Pd-catalyzed enantioselective Michael addition and fluorination reactions of beta-ketoamides. beta-Ketoamide showed higher reactivity than 1,3-diketone and beta-ketoester, though its alpha-proton is likely to be least acidic. Pd enolate formation of beta-ketoamide was much faster than that of beta-ketoester. The crystal structures of (R)-BINAP-Pd-diketone and ketoamide complexes were found to be quite distinct. Pd-diketone complex has bidentate square-planar geometry as have been predicted before, whereas Pd-ketoamide complex was greatly distorted, probably due to steric constraints of the amide bond. (C) 2015 Elsevier Ltd. All rights reserved.