(R)-2-(2,5-dioxo-1-p-tolylpyrrolidin-3-yl)-2-methylpropanal | 1258548-33-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (R)-2-(2,5-dioxo-1-p-tolylpyrrolidin-3-yl)-2-methylpropanal
• 英文别名: 2-(2,5-dioxo-1-(p-tolyl)pyrrolidin-3-yl)-2-methylpropanal；2-methyl-2-[(3R)-1-(4-methylphenyl)-2,5-dioxopyrrolidin-3-yl]propanal
• CAS: 1258548-33-2
• 化学式: C₁₅H₁₇NO₃
• 分子量: 259.305
• InChiKey: LXWXORUVRRXFFX-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  54.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-(4-甲基苯基)-1H-吡咯-2,5-二酮 、 异丁醛 在 1-(((1R,2R)-2-氨基-1,2-二苯乙基)-3-(3,5-双(三氟甲基)苯基)硫脲 作用下， 以 水 为溶剂， 反应 12.0h， 以99%的产率得到(R)-2-(2,5-dioxo-1-p-tolylpyrrolidin-3-yl)-2-methylpropanal
  参考文献：
  名称：

  水介质中对映选择性有机催化异丁醛与马来酰亚胺的迈克尔加成反应

  摘要：

  将硫脲作为有机催化剂引入( R ,R )-1,2-二苯基乙二胺中以促进异丁醛与马来酰亚胺之间的反应。对映选择性迈克尔加成反应是一种使用水作为溶剂的环保方法。由于异丁醛和马来酰亚胺之间的反应，在 0.01 mol% 的低催化剂负载下获得了≥97% 的产率和 99% 的对映选择性。溶剂效应可以通过表明过渡态参与的理论计算来解释，其中 CF 3催化剂的取代基是被周围水分子激活的氢键。这一发现使得在药物应用的手性物质的有机反应中使用低催化剂负载成为可能。此外，提出了有机催化剂对迈克尔反应的溶剂效应，并通过量子计算确定了有机反应机理。

  DOI：

  10.3390/molecules27092759

文献信息

• A highly efficient asymmetric Michael addition of α,α-disubstituted aldehydes to maleimides catalyzed by primary amine thiourea salt
  作者：Feng Yu、Zhichao Jin、Huicai Huang、Tingting Ye、Xinmiao Liang、Jinxing Ye

  DOI：10.1039/c0ob00154f

  日期：——

  The first highly efficient Michael addition of challenging α,α-disubstituted aldehydes to maleimides catalyzed by a simple bifunctional primary amine thiourea catalyst/benzoic acid system has been successfully developed to generate quaternary carbon centers in high yields (up to 99%) with excellent enantioselectivities (91–99%).

  简单的双官能伯胺硫脲催化剂/催化的将高挑战性的α，α-二取代的醛首次高效加成到马来酰亚胺上/苯甲酸 系统已成功开发以生成四元数 碳 中心高收率（高达99％）和出色的对映选择性（91–99％）。
• Asymmetric Michael additions of aldehydes to maleimides using a recyclable fluorous thiourea organocatalyst
  作者：Tsuyoshi Miura、Shohei Nishida、Akira Masuda、Norihiro Tada、Akichika Itoh

  DOI：10.1016/j.tetlet.2011.05.145

  日期：2011.8

  Fluorous thiourea organocatalyst 3 promotes the Michael reaction of aldehydes with maleimides to afford the corresponding adducts in high yields with up to 99% ee. Fluorous organocatalyst 3 can be easily recovered as an insoluble precipitate from the reaction mixture by simple filtration and can be reused without significant loss of catalytic activity.

  氟代硫脲有机催化剂3促进醛与马来酰亚胺的迈克尔反应，以高收率提供相应的加合物，ee最高可达99％。氟有机催化剂3可以通过简单的过滤容易地从反应混合物中以不溶性沉淀物的形式回收，并且可以在不显着损失催化活性的情况下重复使用。
• Highly enantioselective Michael addition of α,α-disubstituted aldehydes to maleimides catalyzed by new primary amine-squaramide bifunctional organocatalysts
  作者：Zhi-wei Ma、Xiao-feng Liu、Jun-tao Liu、Zhi-jing Liu、Jing-chao Tao

  DOI：10.1016/j.tetlet.2017.10.026

  日期：2017.11

  amine-squaramides catalyzed asymmetric Michael addition reaction of α,α-disubstituted aldehydes to maleimides has been developed. This organocatalytic asymmetric reaction provides easy access to functionalized succinimides with a broad substrate scope. Both enantiomers of desired succinimide derivatives were obtained in good to excellent yields (up to 98%) with excellent enantioselectivities (up to >99% ee)

  已开发出新的双官能伯胺-方酸酰胺催化α，α-二取代醛与马来酰亚胺的不对称迈克尔加成反应。这种有机催化不对称反应可轻松获得具有广泛底物范围的官能化琥珀酰亚胺。所需琥珀酰亚胺衍生物的两种对映异构体均以良好至优异的产率（高达98％）和优异的对映选择性（高达> 99％ee）获得。
• Enantioselective Michael Addition of Aldehydes to Maleimides Organocatalyzed by a Chiral Primary Amine-Salicylamide
  作者：Alejandro Torregrosa-Chinillach、Adrien Moragues、Haritz Pérez-Furundarena、Rafael Chinchilla、Enrique Gómez-Bengoa、Gabriela Guillena

  DOI：10.3390/molecules23123299

  日期：——

  amine-salicylamide derived from chiral trans-cyclohexane-1,2-diamine was used as an organocatalyst for the enantioselective conjugate addition of aldehydes, mainly α,α-disubstituted to N-substituted maleimides. The reaction was performed in toluene as a solvent at room temperature. The corresponding enantioenriched adducts were obtained with high yields and enantioselectivities up to 94%. Theoretical calculations

  衍生自手性反式-环己烷-1,2-二胺的伯胺-水杨酰胺用作醛的对映选择性共轭加成的有机催化剂，主要是 α,α-二取代到 N-取代的马来酰亚胺。反应在室温下在甲苯作为溶剂中进行。以高产率和高达 94% 的对映选择性获得了相应的对映体富集的加合物。理论计算用于证明立体感应的合理性。
• Synthesis and catalytic activity of fluorous chiral primary amine-thioureas
  作者：Simonetta Orlandi、Gianluca Pozzi、Mauro Ghisetti、Maurizio Benaglia

  DOI：10.1039/c3nj00807j

  日期：——

  Three enantiopure fluorous thioureas featuring a free –NH2 group were synthesized by direct addition of aromatic isothiocyanates bearing a single n-C8F17 substituent in the ortho, meta and para position, respectively, to enantiopure (1R,2R)-1,2-diaminocyclohexane. The catalytic behavior of these bifunctional molecules was assessed in representative Michael-type reactions. The three fluorous thioureas performed similarly in all the reactions tested, thus showing that the position of the fluorous ponytail does not have a major influence on the catalytic behavior of this class of compounds. In particular, excellent enantioselectivities (up to 99% ee) and yields (up to 98%) were obtained for the addition of aliphatic aldehydes to maleimides to give α-substituted succinimides. Recyclability of these primary amine-based thioureas was found to be limited by the concurrent formation of imine-derivatives during the catalytic process, leading to a structural modification of the organic catalyst.

  通过将分别在正位、偏位和对位具有单个 n-C8F17 取代基的芳香族异硫氰酸酯直接加到对映体 (1R,2R)-1,2-二氨基环己烷上，合成了三种具有游离 -NH2 基团的对映体荧光硫脲。在具有代表性的迈克尔型反应中，对这些双功能分子的催化行为进行了评估。这三种有荧光的硫脲类化合物在所有测试反应中的表现相似，从而表明荧光马尾的位置对这类化合物的催化行为没有重大影响。特别是在脂肪醛与马来酰亚胺的加成反应中，获得了极好的对映选择性（ee高达 99%）和收率（高达 98%），从而得到了 α-取代的琥珀酰亚胺。研究发现，这些伯胺基硫脲的可回收性受到催化过程中同时形成的亚胺衍生物的限制，从而导致有机催化剂结构的改变。