2-(hydroxy(2-nitrophenyl)methyl)cyclopentanone

• 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: 2-(hydroxy(2-nitrophenyl)methyl)cyclopentanone
• 英文别名: (2R)-2-[(S)-hydroxy-(2-nitrophenyl)methyl]cyclopentan-1-one
• 化学式: C₁₂H₁₃NO₄
• 分子量: 235.24
• InChiKey: JOELUJCLBZDDSS-JOYOIKCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  环戊酮 、 邻硝基苯甲醛 在 (S)-2-(3-nitrophenylcarbamoyl)pyrrolidinium bromide 作用下， 以 水 为溶剂， 反应 26.0h， 生成 2-(hydroxy(2-nitrophenyl)methyl)cyclopentanone 、 2-[1-hydroxy-1-(2-nitrophenyl)methyl]cyclopent-1-one
  参考文献：
  名称：

  质子化的（S）-脯氨酰胺衍生物-与水相容的有机催化剂，用于直接不对称羟醛反应

  摘要：

  质子化的手性（S）-脯氨酰胺衍生物已被开发为与水相容的高效有机催化剂，用于直接对映选择性的醛醇缩合反应。由1-脯氨酸和3-硝基苯胺制备的简单质子化的（S）-脯氨酰胺有机催化剂可催化未修饰的酮与多种芳族醛的醛醇缩合反应，以高收率生成醛醇缩合产物，对映选择性高达98％，非对映选择性高达99：1。

  DOI：

  10.1016/j.tetasy.2008.09.020

文献信息

• Organocatalysis with cysteine derivatives: recoverable and cheap chiral catalyst for direct aldol reactions
  作者：Shi Li、Xiangkai Fu、Chuanlong Wu

  DOI：10.1007/s11164-011-0336-5

  日期：2012.1

  Highly enantioselective, recoverable and cheap cysteine derivatives have been developed with improved solubility properties in common, nonpolar organic solvents. The reactions were catalyzed using 5 mol% 1e, and the aldol products could be obtained with up to 99:1 syn/anti ratio and >99% ee. The catalyst could be easily recovered and reused, with only a slight decrease of enantioselectivity observed for five cycles. Catalyst 1e can be efficiently used in large-scale reactions with enantioselectivity being maintained at the same level, which offers great possibility for application in industry. (i) Direct aldol reactions proceeded in 1,2-dichloroethane using simple procedures. (ii) Direct S-acylation of cysteine to give organocatalysts 1a–f can be economically carried out easily in a single step from commercially available sources, with both enantiomers being readily available. (iii) 5 mol% catalyst 1e was sufficient to furnish the aldol products in excellent yields (up to 93%) and enantioselectivities (up to 99%). (iv) Catalyst 1e could be easily recovered and reused, and also can be efficiently used in large-scale reactions with enantioselectivity being maintained at the same level, which offers great possibility for applications in industry.

  开发了一种高度对映选择性、可回收且廉价的半胱氨酸衍生物，其在常见的非极性有机溶剂中具有改善的溶解性特性。反应使用5 mol%催化剂1e进行催化，醛醇产物的syn/anti比率可高达99:1，对映体过量（ee）超过99%。催化剂可以轻松回收并重复使用，经过五个循环后仅观察到轻微的对映选择性降低。催化剂1e可以在大规模反应中有效使用，并维持相同水平的对映选择性，这为其在工业中的应用提供了很大可能性。(i) 直接醛醇反应在1,2-二氯乙烷中通过简单的程序进行。(ii) 半胱氨酸的直接S-酰化以获得有机催化剂1a-f，可以轻松地从商业来源通过一步经济地进行，两种对映体均易于获得。(iii) 5 mol%催化剂1e足以以优异的产率（高达93%）和对映选择性（高达99%）提供醛醇产物。(iv) 催化剂1e可以轻松回收和重复使用，并且可以在大规模反应中有效使用，保持相同水平的对映选择性，这为其在工业中的应用提供了极大的可能性。
• Direct asymmetric aldol reactions between aldehydes and ketones catalyzed by l-tryptophan in the presence of water
  作者：Zhaoqin Jiang、Hui Yang、Xiao Han、Jie Luo、Ming Wah Wong、Yixin Lu

  DOI：10.1039/b921460g

  日期：——

  Primary amino acids and their derivatives were investigated as catalysts for the direct asymmetric aldol reactions between ketones and aldehydes in the presence of water, and L-tryptophan was shown to be the best catalyst. Solvent effects, substrate scope and the influence of water on the reactions were investigated. Quantum chemical calculations were performed to understand the origin of the observed

  研究了伯氨基酸及其衍生物作为在水存在下酮与醛之间直接不对称醛醇缩合反应的催化剂，L-色氨酸是最好的催化剂。研究了溶剂效应，底物范围和水对反应的影响。进行量子化学计算以了解观察到的立体选择性的起源。
• Homogeneous silicone modified primary amine-Brønsted acid salt catalyzed aldol reaction: unexpected synergistic effect of polysiloxane with remarkable improvement of efficiency and stereoselectivity
  作者：Li-Wen Xu、Ya-Dong Ju、Li Li、Hua-Yu Qiu、Jian-Xiong Jiang、Guo-Qiao Lai

  DOI：10.1016/j.tetlet.2008.09.145

  日期：2008.12

  We have developed a new strategy to improve the stereoselectivity in enamine catalysis by the introduction of super-hydrophobic long-chain silicone/polysiloxane as support/functional group for a model aldol reaction. The homogeneous direct aldol reaction of cyclic ketones with different aromatic aldehydes catalyzed by polysiloxane-derived primary amines has been reported with high yields, good diastereoselectivity

  我们已经开发出一种新的策略，通过引入超疏水长链有机硅/聚硅氧烷作为模型醇醛反应的载体/官能团，来提高烯胺催化的立体选择性。已经报道了由聚硅氧烷衍生的伯胺催化的环状酮与不同芳族醛的均相直接羟醛反应，具有高收率，良好的非对映选择性和高达99％的ee。
• Linear polystyrene anchored l-proline, new recyclable organocatalysts for the aldol reaction in the presence of water
  作者：Yu-Xia Liu、Ya-Nan Sun、Hao-Han Tan、Wei Liu、Jing-Chao Tao

  DOI：10.1016/j.tetasy.2007.10.032

  日期：2007.11

  anchored catalysts 1a and 1b have been synthesized efficiently. The catalytic activities and stereoselectivity of these readily tunable and amphiphilic organocatalysts were evaluated in the direct asymmetric aldol reaction of various aromatic aldehydes and ketones. By using 5 mol % of the catalysts, the corresponding products of the aldol reaction were obtained in good yields (up to 94%) and with excellent

  已经有效地合成了两种基于l-脯氨酸的线性聚苯乙烯锚定的催化剂1a和1b。在各种芳族醛和酮的直接不对称醛醇缩合反应中评估了这些易于调节且两亲的有机催化剂的催化活性和立体选择性。通过使用5mol％的催化剂，在DMF中以良好的收率（高达94％）和优异的抗非对映选择性（高达96∶4）和对映选择性（高达96％ee）获得了醛醇缩合反应的相应产物。在水的存在下。在酮/水混合物中，这些反应的产率低于在湿DMF中的产率（最高为76％）。但是，立体选择性相当（高达93：7抗/合成比和95％ee）。另外，可以通过简单的沉淀和过滤过程来回收催化剂1a和1b。它们也可以重复使用至少五次，而不会明显降低催化效率。
• Preparation of Immobilized L-Prolinamide Via Enzymatic Polymerization of Phenolic L-Prolinamide and Evaluation of Its Catalytic Performance for Direct Asymmetric Aldol Reaction
  作者：Chengke Qu、Wenshan Zhao、Lei Zhang、Yuanchen Cui

  DOI：10.1002/chir.22302

  日期：2014.4

  L‐prolinamide. The catalytic performance of the resultant polymer‐supported L‐prolinamide for direct asymmetric aldol reaction between aromatic aldehyde and cyclohexanone was studied. The results show that as prepared L‐prolinamide can catalyze the aldol reaction at room temperature in the presence of H2O. Relevant aldol addition products are obtained with good yields (up to 91%), high diastereoselectivities

  允许以辣根过氧化物酶为催化剂参与酚L-脯氨酰胺的酶促聚合反应，生成固定化的L-脯氨酰胺。研究了所得聚合物负载的L-脯氨酰胺对芳族醛与环己酮之间直接不对称羟醛反应的催化性能。结果表明，制得的L-脯氨酰胺可在H 2 O存在下在室温下催化羟醛反应。获得了相关的羟醛加成产物，收率高（高达91％），高非对映选择性（高达6:94 dr ）和中等对映选择性（最高87％ee）。此外，标题聚合物负载的催化剂可以回收并重复使用至少五个循环，而活性几乎保持不变。手性26：209–213，2014年。©2014 Wiley Periodicals，Inc.