(S)-3-(2-chlorophenyl)-2,2-dimethyl-4-nitrobutanal | 1227459-45-1

• 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)-3-(2-chlorophenyl)-2,2-dimethyl-4-nitrobutanal
• 英文别名: (3S)-3-(2-chlorophenyl)-2,2-dimethyl-4-nitrobutanal
• CAS: 1227459-45-1
• 化学式: C₁₂H₁₄ClNO₃
• 分子量: 255.701
• InChiKey: UENAIURQSOHLFG-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  1-chloro-2-(2-nitrovinyl)benzene 、 异丁醛 在 1-((1R,2R)-2-aminocyclohexyl)-3-(1²,3²,5²,7²-tetrapropoxy-1,3,5,7(1,3)-tetrabenzenacyclooctaphane-1⁵-yl)thiourea 作用下， 反应 75.0h， 以57%的产率得到(S)-3-(2-chlorophenyl)-2,2-dimethyl-4-nitrobutanal
  参考文献：
  名称：

  基于杯芳烃的伯胺硫脲催化的无溶剂对映选择性迈克尔反应

  摘要：

  为了研究其在对映选择性迈克尔加成反应中的催化能力，合成了安装在（R，R）-1,2-环己二胺支架上的上边缘功能化杯[4]芳烃基硫脲。发现反应在无溶剂条件下方便地进行，观察到良好至高对映选择性。根据这项初步研究，杯芳烃[4]芳烃单元可能会通过范德华接触和C–H···π相互作用与范德华接触并在较小程度上影响反应的立体化学结果，从而影响转化率。基材。

  DOI：

  10.1021/acs.joc.8b01454

文献信息

• Asymmetric Conjugate Addition of α,α-Disubstituted Aldehydes to Nitroalkenes Organocatalyzed by Chiral Monosalicylamides from trans-Cyclohexane-1,2-Diamines
  作者：José Martínez-Guillén、Jesús Flores-Ferrándiz、Cecilia Gómez、Enrique Gómez-Bengoa、Rafael Chinchilla

  DOI：10.3390/molecules23010141

  日期：——

  Primary amine-salicylamides derived from chiral trans-cyclohexane-1,2-diamines are used as organocatalysts for the enantioselective conjugate addition of α,α-disubstituted aldehydes to arylated and heteroarylated nitroalkenes. The reaction is performed in the presence of 4-dimethylaminopyridine as an additive in dichloromethane as a solvent at room temperature. The corresponding enantioenriched γ-nitroaldehydes

  衍生自手性反式-环己烷-1,2-二胺的伯胺-水杨酰胺用作有机催化剂，用于将 α,α-二取代醛对映选择性共轭加成到芳基化和杂芳基化硝基烯烃。该反应在作为添加剂的4-二甲氨基吡啶存在下在作为溶剂的二氯甲烷中在室温下进行。以高达 95% 的对映选择性获得相应的对映体富集的 γ-硝基醛。理论计算用于证明立体感应的原因。
• Magnetic Nanoparticles-Supported Chiral Catalyst with an Imidazolium Ionic Moiety: An Efficient and Recyclable Catalyst for Asymmetric Michael and Aldol Reactions
  作者：Anguo Ying、Shuo Liu、Zhifeng Li、Gang Chen、Jianguo Yang、Hua Yan、Songlin Xu

  DOI：10.1002/adsc.201600145

  日期：2016.6.30

  only in the enantioselective Michael addition but also in the asymmetric aldol condensation to afford good to excellent yields (70–94%) and satisfactory stereoselectivity (ee: 92–100%, dr: 91:9–99:1).The role of the ionic moiety was verified by comparison of the catalyst with an ionic moiety‐free counterpart. The heterogeneous catalyst was easily separated and recovered using external magnetic force

  制备了由咪唑离子部分改性的磁性纳米粒子支撑的手性氨基环己烷与硫酰胺的混合物，并通过傅立叶变换红外光谱（FT-IR），X射线衍射（XRD），透射电子显微镜（TEM）对其进行了表征，振动样品磁力分析（VSM），热重分析（TG）分析和元素分析。该催化剂不仅成功地用于对映选择性迈克尔加成反应中，而且还成功地应用于不对称的羟醛缩合反应中，具有良好至优异的收率（70–94％）和令人满意的立体选择性（ee：92–100％，博士：91：9–99：1）。通过比较催化剂与无离子部分的对应物，验证了离子部分的作用。该多相催化剂很容易利用外部磁力进行分离和回收，最多可使用五次，而不会明显降低其催化活性。
• Highly enantioselective Michael addition of isobutyraldehyde to nitroalkenes
  作者：Tianxiong He、Qing Gu、Xin-Yan Wu

  DOI：10.1016/j.tet.2010.02.069

  日期：2010.4

  The asymmetric catalytic Michael reaction between isobutyraldehyde and nitroalkanes with chiral primary amine thiourea organocatalysts was described. In the presence of 10 mol % of 1-((1R,2R)-2-amino-1,2-diphenylethyl)-3-benzylthiourea, the desired products were achieved in excellent enantioselectivity (up to>99% ee) with up to 98% yield.

  描述了异丁醛与硝基烷烃与手性伯胺硫脲有机催化剂之间的不对称催化迈克尔反应。在10摩尔％的1-（（1 R，2 R）-2-氨基-1,2-二苯乙基）-3-苄基硫脲的存在下，所需的产物以优异的对映选择性（最高> 99％ee）得到收率高达98％。
• Highly asymmetric Michael additions of α,α-disubstituted aldehydes to β-nitroalkenes promoted by chiral pyrrolidine–thiourea bifunctional catalysts
  作者：Jian-Fei Bai、Xiao-Ying Xu、Qing-Chun Huang、Lin Peng、Li-Xin Wang

  DOI：10.1016/j.tetlet.2010.03.039

  日期：2010.5

  A series of secondary amine–thiourea catalysts derived from l-proline and chiral diamine were prepared and first applied to the Michael addition of α,α-disubstituted aldehydes to trans-β-nitroalkenes. Moderate yields (47–75%) and excellent enantioselectivities (up to 96% ee) were obtained for a variety of aryl and heteroaryl nitroalkenes.

  制备了一系列衍生自1-脯氨酸和手性二胺的仲胺-硫脲催化剂，并将其首先用于将α，α-二取代醛与反式-β-硝基烯烃进行迈克尔加成反应。对于各种芳基和杂芳基硝基烯烃，均获得中等收率（47–75％）和出色的对映选择性（高达96％ee）。
• In search of diamine analogs of the α,α-diphenyl prolinol privileged chiral organocatalyst. Synthesis of diamine derivatives of α,α-diphenyl-(S)-prolinol and their application as organocatalysts in the asymmetric Michael and Mannich reactions
  作者：Gloria Reyes-Rangel、Jorge Vargas-Caporali、Eusebio Juaristi

  DOI：10.1016/j.tet.2015.11.032

  日期：2016.1

  This paper describes improved reaction conditions for the substitution of the hydroxyl group in (S)-diphenyl(pyrrolidin-2-yl)methanol by the azide group, which was then reduced to the diamine derivative. We examined two protecting groups (N-Bn and N-Boc) on the pyrrolidine nitrogen in order to functionalize the primary amino group into various amide, alkylated amine, sulfonamide, thiourea and triazole derivatives. Notably, carefully controlled conditions were required to generate the desired derivatives from the sterically hindered benzhydrylamine moiety. Unexpectedly, upon removal of the N-protecting group in derivatives containing electrophilic polar double bonds (C=S, C=O) cyclization took place, affording products such as amidines. The target compounds were evaluated as bifunctional organocatalysts in the asymmetric Michael and Mannich addition reactions. (S)-2-(Azidodiphenylmethyl) pyrrolidine (S)-7 was identified as the most efficient organocatalyst among the various diamine derivatives of alpha,alpha-diphenyl-(S)-prolinol prepared in this work. (C) 2015 Elsevier Ltd. All rights reserved.