(S)-2-((R)-hydroxy(2,4-dinitrophenyl)methyl)cyclohexan-1-one | 1068139-51-4

• 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: (S)-2-((R)-hydroxy(2,4-dinitrophenyl)methyl)cyclohexan-1-one
• 英文别名: (S)-2-[(R)-hydroxyl(2,4-nitrophenyl)methyl]cyclohexanone；(S)-2-[(R)-hydroxy-(2,4-dinitrophenyl)methyl]cyclohexanone；2-((2,4-dinitrophenyl)(hydroxy)methyl)cyclohexanone；(2S)-2-[(R)-hydroxy-(2,4-dinitro-phenyl)methyl]cyclohexan-1-one；2-[hydroxy(2,4-dinitrophenyl)methyl]cyclohexan-1-one；(2S)-2-[(R)-(2,4-dinitrophenyl)-hydroxymethyl]cyclohexan-1-one
• CAS: 1068139-51-4
• 化学式: C₁₃H₁₄N₂O₆
• 分子量: 294.264
• InChiKey: BMYVISFAXKXOLL-MFKMUULPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  129
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2,4-二硝基苯甲醛 、 环己酮 在 (S)-N-(4-十二烷基苯磺酰基)吡咯烷-2-甲酰胺 、 水 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 72.0h， 以51%的产率得到(S)-2-((R)-hydroxy(2,4-dinitrophenyl)methyl)cyclohexan-1-one
  参考文献：
  名称：

  使用 N-(对十二烷基苯磺酰基)-2-吡咯烷甲酰胺进行高度立体选择性和可扩展的抗羟醛反应：立体选择性的范围和起源

  摘要：

  一种由脯氨酸模拟物N- (对十二烷基苯磺酰基)-2-吡咯烷甲酰胺催化的高度对映和非对映选择性反羟醛过程（高达 >99% ee，>99:1 dr）已被开发出来。可以使用低至2mol%的催化剂负载。已经证明可以使用工业友好型溶剂进行这种转化以及纯净的反应条件。探索了这种对一系列醛和酮的转化范围。密度泛函理论计算表明，增强的非对映选择性的起源是由于磺酰胺、亲电子试剂和催化剂烯胺之间存在非经典氢键，有利于 Houk−List 模型中主要的反 Re 醛醇TS 。

  DOI：

  10.1021/jo1015008

文献信息

• SULFONAMIDE-BASED ORGANOCATALYSTS AND METHOD FOR THEIR USE
  申请人：Carter Rich Garrett

  公开号：US20100184986A1

  公开（公告）日：2010-07-22

  Organocatalysts, particularly proline sulfonamide organocatalysts, having a first general formula as follows are disclosed. Embodiments of a method for using these organocatalysts also are disclosed. The method comprises providing a disclosed organocatalyst, and performing a reaction, often an enantioselective or diastereoselective reaction, using the organocatalyst. Solely by way of example, disclosed catalysts can be used to perform aldol reactions, conjugate additions, Michael additions, Robinson annulations, Mannich reactions, α-aminooxylations, α-hydroxyaminations, α-aminations and alkylation reactions. Certain of such reactions are intramolecular cyclizations used to form cyclic compounds, such as 5- or 6-membered rings, having one or more chiral centers. Disclosed organocatalysts generally are much more soluble in typical solvents used for organic synthesis than are known compounds. Moreover, the reaction yield is generally quite good with disclosed compounds, as is their enantioselective and diastereoselective effectiveness.

  披露了具有如下一般公式之一的有机催化剂，尤其是脯氨酸磺酰胺有机催化剂。还披露了使用这些有机催化剂的方法的实施例。该方法包括提供一种披露的有机催化剂，并使用该有机催化剂进行反应，通常是立体选择性的反应或对映选择性反应。仅作为示例，披露的催化剂可用于进行aldol反应、共轭加成、Michael加成、Robinson环化反应、Mannich反应、α-氨基氧化、α-羟基胺化、α-胺化和烷基化反应。其中一些反应是分子内环化反应，用于形成具有一个或多个手性中心的环状化合物，例如5或6元环。披露的有机催化剂通常比已知的化合物更容易溶于用于有机合成的典型溶剂中。此外，使用披露化合物的反应收率通常相当好，它们的对映选择性和非对映选择性效果也很好。
• 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。
• 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.
• <i>N</i>-(<i>p</i>-Dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide: A Practical Proline Mimetic for Facilitating Enantioselective Aldol Reactions
  作者：Hua Yang、Rich G. Carter

  DOI：10.1021/ol801941j

  日期：2008.10.16

  A highly practical and readily available proline surrogate has been developed with improved solubility properties in common, nonpolar organic solvents. This sulfonamide-based catalyst has proven highly effective at facilitating enantioselective and diastereoselective aldol reactions with a range of substrates in nonpolar organic solvents in the presence of a single equivalent of water. Additionally

  一种高度实用且易于获得的脯氨酸替代品已被开发出来，其在常见非极性有机溶剂中的溶解度得到改善。事实证明，这种磺酰胺基催化剂在单当量水存在下，在非极性有机溶剂中能够非常有效地促进与一系列底物的对映选择性和非对映选择性羟醛反应。此外，在不存在任何有机溶剂的情况下，可以使用低至 2 mol% 的催化剂负载，并具有持续的高水平选择性。
• New simple and recyclable O-acylation serine derivatives as highly enantioselective catalysts for the large-scale asymmetric direct aldol reactions in the presence of water
  作者：Chuanlong Wu、Xiangkai Fu、Shi Li

  DOI：10.1016/j.tet.2011.03.083

  日期：2011.6

  products in high yields (up to 99%) and enantioselectivities (up to 99% ee). The catalyst 1b can be easily recovered and reused, and without significant decrease of enantioselectivity was observed for five cycles. This novel catalyst can be efficiently used in large-scale reactions with the enantioselectivities being maintained at the same level, which offers a great possibility for application in industry

  通过在室温下在三氟乙酸中将丝氨酸与酰氯合理结合，一步合成了新型的O-酰化丝氨酸衍生的有机催化剂。任何步骤均不涉及保护基团或色谱技术，某些组合的丝氨酸表面活性剂有机催化剂可介导酮与一系列芳香醛的直接羟醛反应，从而以高收率（高达99％）和对映选择性提供羟醛产物。 （最高99％ee）。催化剂1b可以容易地回收和再利用，并且在五个循环中未观察到对映选择性的显着降低。这种新催化剂可以有效地用于大规模反应，同时将对映选择性保持在同一水平，这为工业应用提供了很大的可能性。