(3S,4S)-4-hydroxy-3-methyl-4-(4-nitrophenyl)butan-2-one

• 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: (3S,4S)-4-hydroxy-3-methyl-4-(4-nitrophenyl)butan-2-one
• 英文别名: 4-hydroxy-3-methyl-4-(4-nitrophenyl)-butan-2-one
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: SHQWHOLGKWLWAN-HQJQHLMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  83.1
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对硝基苯甲醛 、 丁酮 在 C₄₇H₈₀N₂O₃₄ 作用下， 反应 96.0h， 生成 (3S,4S)-4-hydroxy-3-methyl-4-(4-nitrophenyl)butan-2-one 、 (3R,4R)-4-hydroxy-3-methyl-4-(4-nitrophenyl)butan-2-one
  参考文献：
  名称：

  Biomimetic asymmetric aldol reactions catalyzed by proline derivatives attached to β-cyclodextrin in water

  摘要：

  Two proline derivatives, (S)-2-aminomethylpyrrolidine and (R)-2-aminomethylpyrrolidine modified beta-CD (CD-1, CD-2) were synthesized in the yields of 31% and 14%. Their self-inclusion conformations were characterized by H-1 ROESY NMR studies and quantum calculation. When CD-1 was applied to asymmetric aldol reactions, up to 94% ee was obtained. Substrate selectivity was also observed in these asymmetric aldol reactions. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2012.04.140

文献信息

• Readily Tunable and Bifunctional <scp>l</scp>-Prolinamide Derivatives:  Design and Application in the Direct Enantioselective Aldol Reactions
  作者：Jia-Rong Chen、Hai-Hua Lu、Xin-Yong Li、Lin Cheng、Jian Wan、Wen-Jing Xiao

  DOI：10.1021/ol0520323

  日期：2005.9.1

  [reaction: see text] Readily tunable and bifunctional L-prolinamides as novel organocatalysts have been developed, and their catalytic activities were evaluated in the direct asymmetric Aldol reactions of various aromatic aldehydes and cyclohexanone. High isolated yields (up to 94%), enantioselectivities (up to 99% ee), and anti-diastereoselectivities (up to 99:1) were obtained under the optimal conditions

  [反应：见正文]已开发出易于调节的双功能L-脯氨酰胺作为新型有机催化剂，并在各种芳族醛和环己酮的直接不对称Aldol反应中评估了它们的催化活性。在最佳条件下，获得了高分离产率（高达94％），对映选择性（高达99％ee）和抗非对映选择性（高达99：1）。
• Chiral Primary−Tertiary Diamine Catalysts Derived From Natural Amino Acids for <i>syn</i>-Aldol Reactions of Hydroxy Ketones
  作者：Jiuyuan Li、Sanzhong Luo、Jin-Pei Cheng

  DOI：10.1021/jo802557p

  日期：2009.2.20

  A series of primary-tertiary diamine catalysts were designed and synthesized from primary natural amino acids. Application of these new chiral catalysts in direct aldol reactions of α-hydroxyketones showed very good catalytic activity (up to 97% yield) and high syn selectivity (up to syn/ anti = 30:1, 99% ee).

  从伯天然氨基酸设计合成了一系列伯叔二胺催化剂。这些新的手性催化剂在α-羟基酮的直接醛醇缩合反应中的应用显示出非常好的催化活性（高达97％的收率）和高的合成选择性（高达syn / anti = 30：1，99％ee）。
• Direct Asymmetric Aldol Reaction Catalyzed by C2-Symmetrical Chiral Primary Amine Organocatalysts
  作者：Gong-Jian Zhu、Chao-Shan Da、Ya-Ning Jia、Xiao Ma、Lei Yi

  DOI：10.2174/157017810790533904

  日期：2010.1.1

  C-2-symmetrical chiral primary amines were synthesized from chiral BINOL and diamines. Then their catalytic activities in the asymmetric aldol reactions were evaluated, and the result indicated that 1c was the optimal organocatalyst. The reaction of a variety of aromatic aldehydes with aliphatic ketones, catalyzed by 20 mol % 1c in the addition of benzoic acid in carbon tetrachloride, afforded the aldol products

  从手性 BINOL 和二胺合成了三种新型 C-2 对称手性伯胺。然后评估了它们在不对称醛醇反应中的催化活性，结果表明1c是最佳的有机催化剂。在四氯化碳中加入苯甲酸，在 20 mol % 1c 的催化下，多种芳香醛与脂肪族酮反应得到高产率（高达 92%）和良好的对映选择性（高达 71%）的醛醇产物.
• Asymmetric Aldol Reaction Catalyzed by the Anion of an Ionic Liquid
  作者：Vincent Gauchot、Andreea R. Schmitzer

  DOI：10.1021/jo300737u

  日期：2012.6.1

  its applications as a catalyst for the asymmetric aldol reaction. By performing the aldol reaction in [Bmim]NTf2 as a solvent, we report excellent isolated yields of the aldol product (up to 99%), as well as modest to excellent selectivities (dr superior to 99:1. ee up to 89%). Mechanistic insights and the origins of the selectivity of the aldol reaction are discussed on the basis of the results obtained

  本文中，我们报道了衍生自反式-1-羟基脯氨酸的手性咪唑盐的合成及其作为不对称羟醛反应的催化剂的应用。通过在[Bmim] NTf 2中作为溶剂进行羟醛反应，我们报告了羟醛产物的优良分离产率（高达99％），以及中等至优异的选择性（dr优于99：1 ee高达89） ％）。基于两种具有不同氢键电势的​​催化咪唑盐获得的结果，讨论了机械学见解和醛醇缩合反应选择性的起源。
• 2,4-Dinitrophenol as an Effective Cocatalyst: Greatly Improving the Activities and Enantioselectivities of Primary Amine Organocatalysts for Asymmetric Aldol Reactions
  作者：Chao-Shan Da、Li-Ping Che、Qi-Peng Guo、Feng-Chun Wu、Xiao Ma、Ya-Ning Jia

  DOI：10.1021/jo802758b

  日期：2009.3.20

  Seven primary amine organocatalysts 1a−g were readily prepared from natural primary amino acids via two steps and then were used to catalyze the direct asymmetric aldol reaction, but they showed very poor enantioselectivities and activities. As an effective cocatalyst, 2,4-dinitrophenol (DNP) dramatically elevated the activities and enantioselectivities of these very inefficient primary amine organocatalysts

  可以通过两步从天然伯氨基酸容易地制备出7种伯胺有机催化剂1a - g，然后将其用于催化直接不对称羟醛反应，但它们的对映选择性和活性非常差。作为一种有效的助催化剂，2,4-二硝基苯酚（DNP）大大提高了这些非常低效的伯胺有机催化剂的活性和对映选择性。与从头开发催化剂相比，通过选择和使用最佳助催化剂对非常低效的有机催化剂进行这种补救的过程特别具有成本效益且对环境有利。由1f组成的最高效的有机催化系统DNP表现出高的对映选择性和良好的非对映选择性，具有广谱的七种酮。线性酮和环戊酮主要合成产物，而环己酮主要产生反产物。