(R)-4-nitro-3-(4-nitrophenyl)-1-phenylbutan-1-one | 1194795-70-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: (R)-4-nitro-3-(4-nitrophenyl)-1-phenylbutan-1-one
• 英文别名: (3R)-4-nitro-3-(4-nitrophenyl)-1-phenylbutan-1-one
• CAS: 1194795-70-4
• 化学式: C₁₆H₁₄N₂O₅
• 分子量: 314.298
• InChiKey: VQNGFFCDFCPMQU-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  109
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1-nitro-4-[(E)-2-nitroeth-1-enyl]benzene 、 苯乙酮 在 (S)-di-tert-butyl 2-{3-[(1S,2S)-2-amino-1,2-diphenylethyl]thioureido}succinate 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以61%的产率得到(R)-4-nitro-3-(4-nitrophenyl)-1-phenylbutan-1-one
  参考文献：
  名称：

  基于天然氨基酸叔丁基酯的伯胺-硫脲作为迈克尔反应的有机催化剂

  摘要：

  Abstractmagnified imageA new class of primary amine‐thioureas based on tert‐butyl esters of (S)‐α‐amino acids and (1S,2S)‐diphenylethylenediamine was synthesized and their activity as catalysts in Michael additions was evaluated. Derivatives based on di‐tert‐butyl aspartate and tert‐butyl O‐tert‐butyl threoninate provided the product of the reaction between trans‐β‐nitrostyrene and acetone in quantitative yield and high enantioselectivity (87–91% ee). All the thioureas based on tert‐butyl esters of amino acids catalyzed the reaction of nitroolefins with acetophenone with high enantioselectivity (92–98% ee). Thus, low‐cost, commercially available tert‐butyl esters of natural amino acids are very important chiral building blocks for the construction of novel chiral thioureas able to catalyze asymmetric Michael additions with high enantioselectivity.

  DOI：

  10.1002/adsc.200800812

文献信息

• Enantioselective Conjugate Addition of Nitro Compounds to α,β-Unsaturated Ketones: An Experimental and Computational Study
  作者：Rubén Manzano、José M. Andrés、Rosana Álvarez、María D. Muruzábal、Ángel R. de Lera、Rafael Pedrosa

  DOI：10.1002/chem.201100241

  日期：2011.5.16

  thioureas derived from easily available diamines, prepared from α‐amino acids, have been tested as catalysts in the enantioselective Michael additions of nitroalkanes to α,β‐unsaturated ketones. The best results are obtained with the bifunctional catalyst prepared from L‐valine. This thiourea promotes the reaction with high enantioselectivities and chemical yields for aryl/vinyl ketones, but the enantiomeric

  在由α-氨基酸制得的易得的二胺中衍生出一系列手性硫脲，已对硝基烷烃向α，β-不饱和酮的对映选择性迈克尔加成反应中的催化剂进行了测试。用L-缬氨酸制备的双功能催化剂可获得最佳结果。该硫脲对芳基/乙烯基酮具有高的对映选择性和化学收率，促进了反应，但是烷基/乙烯基衍生物的对映体比例非常适中。取代的硝基甲烷的加入导致相应的加合物具有优异的对映选择性，但非对映选择性非常差。查尔酮与[D 3硝基甲烷，表明最终加成产物在反应条件下发生差向异构。差向异构体解释了在形成具有两个相邻的叔立体中心的加合物时观察到的低非对映选择性。在B3LYP / 3-21G *的水平上，已经进行了对应于硝基烷和α，β-不饱和酮的两种替代活化方式的过渡结构的密度泛函研究。该计算与反应模型一致，该模型涉及将硫脲活化的硝酸酯迈克尔加成到有机催化剂的质子化胺活化的酮上。通过计算预测的对映选择性与对芳基和烷基取代的α，β-不饱和酮的实验值一致。
• Organocatalyzed highly stereoselective Michael addition of ketones to alkylidene malonates and nitroolefins using chiral primary-secondary diamine catalysts based on bispidine
  作者：Jie Liu、Zhigang Yang、Xiaohua Liu、Zhen Wang、Yanling Liu、Sha Bai、Lili Lin、Xiaoming Feng

  DOI：10.1039/b910939k

  日期：——

  based on bispidine have been developed to catalyze the asymmetric Michael addition of ketones to alkylidene malonates and nitroalkenes. The corresponding products were obtained in high yields (up to 99%) with high diastereoselectivities (up to 99:1) and high enantioselectivities (up to 97% ee) under mild conditions using either environmentally benign water as the solvent or no solvent.

  已经开发了包含基于联吡啶的伯-仲二胺的有机催化剂以催化酮向亚烷基丙二酸酯和硝基烯烃的不对称迈克尔加成。在温和条件下使用环境友好的方法，可以以高收率（高达99％），高非对映选择性（高达99：1）和高对映选择性（高达97％ee）获得相应的产物。水 作为溶剂或不使用溶剂。
• Enantioselective addition of aryl ketones and acetone to nitroalkenes organocatalyzed by carbamate-monoprotected cyclohexa-1,2-diamines
  作者：Jesús Flores-Ferrándiz、Alexander Stiven、Lia Sotorríos、Enrique Gómez-Bengoa、Rafael Chinchilla

  DOI：10.1016/j.tetasy.2015.07.011

  日期：2015.9

  Enantiomerically pure carbamate-monoprotected trans-cyclohexane-1,2-diamines are used as chiral organocatalysts for the addition of aryl ketones and acetone to nitroalkenes to give enantioenriched beta-substituted gamma-nitroketones. The reaction was performed in the presence of 3,4-dimethoxybenzoic acid as an additive, in chloroform as the solvent at room temperature, achieving enantioselectivities up to 96%. Theoretical calculations are used to justify the observed sense of the stereoinduction. (C) 2015 Elsevier Ltd. All rights reserved.
• Primary Amine-Thioureas based on<i>tert</i>-Butyl Esters of Natural Amino Acids as Organocatalysts for the Michael Reaction
  作者：Christoforos G. Kokotos、George Kokotos

  DOI：10.1002/adsc.200800812

  日期：2009.6

  Abstractmagnified imageA new class of primary amine‐thioureas based on tert‐butyl esters of (S)‐α‐amino acids and (1S,2S)‐diphenylethylenediamine was synthesized and their activity as catalysts in Michael additions was evaluated. Derivatives based on di‐tert‐butyl aspartate and tert‐butyl O‐tert‐butyl threoninate provided the product of the reaction between trans‐β‐nitrostyrene and acetone in quantitative yield and high enantioselectivity (87–91% ee). All the thioureas based on tert‐butyl esters of amino acids catalyzed the reaction of nitroolefins with acetophenone with high enantioselectivity (92–98% ee). Thus, low‐cost, commercially available tert‐butyl esters of natural amino acids are very important chiral building blocks for the construction of novel chiral thioureas able to catalyze asymmetric Michael additions with high enantioselectivity.