ethyl 2-methyl-2-nitro-5-oxo-3-phenylcyclohexanecarboxylate

• 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: ethyl 2-methyl-2-nitro-5-oxo-3-phenylcyclohexanecarboxylate
• 英文别名: ethyl (1R,2S,3R)-2-methyl-2-nitro-5-oxo-3-phenylcyclohexane-1-carboxylate
• 化学式: C₁₆H₁₉NO₅
• 分子量: 305.331
• InChiKey: VZKZUWKZOHOSFE-YCPHGPKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  89.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  α-Hydroxy-β-nitro-buttersaeure-aethylester 在 9-amino(9-deoxy)epi-quinine 、 甲基磺酰氯 、 三乙胺 、 水杨酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.25h， 生成 ethyl 2-methyl-2-nitro-5-oxo-3-phenylcyclohexanecarboxylate 、 ethyl 2-methyl-2-nitro-5-oxo-3-phenylcyclohexanecarboxylate 、 ethyl 2-methyl-2-nitro-5-oxo-3-phenylcyclohexanecarboxylate
  参考文献：
  名称：

  Synthesis of highly decorated chiral 2-nitro-cyclohexane carboxylic esters through microwave-assisted organocatalyzed cascade reactions

  摘要：

  Starting from (E)-beta-substituted-beta-nitroacrylates and alpha,beta-unsaturated ketones, a stereoselective organo-catalyzed one-pot methodology allowed to synthesize highly decorated chiral 2-nitro-cyclohexane carboxylic esters. The reaction is promoted by Cinchona alkaloid-derived primary amines in the presence of an acidic co-catalyst and affords two diastereoisomers, in good yields and high enantiomeric excess (often higher than 90% ee). By replacing conventional heating with microwave irradiation, cleaner reactions in shortened times (from 48 h to 30 min) were obtained, with improved dr (80:20) and high ee (up to 94%). The application of microwave technology to this organocatalytic methodology allowed also employing Cl substituted enones, leading to cyclohexanones with four contiguous stereocenters in two isomers only, and up to 99% enantioselectivity. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2014.10.073

文献信息

• Stereoselective organocatalysed reactions in deep eutectic solvents: highly tunable and biorenewable reaction media for sustainable organic synthesis
  作者：Elisabetta Massolo、Silvia Palmieri、Maurizio Benaglia、Vito Capriati、Filippo M. Perna

  DOI：10.1039/c5gc01855b

  日期：——

  Different metal-free catalytic enantioselective reactions have been performed in high yields and enantioselectivity in natural, biorenewable and environmentally-friendly DESs. The recyclability of the chiral catalyst by a simple extraction protocol was also successfully accomplished.

  在天然、生物可再生和环境友好的深度共熔溶剂中，进行了不同的无金属催化不对称反应，产率高且对映选择性好。通过简单的萃取方法成功实现了手性催化剂的可回收利用。
• Solid Supported 9-Amino-9-deoxy-<i>epi</i>-quinine as Efficient Organocatalyst for Stereoselective Reactions in Batch and Under Continuous Flow Conditions
  作者：Riccardo Porta、Maurizio Benaglia、Francesca Coccia、Franco Cozzi、Alessandra Puglisi

  DOI：10.1002/adsc.201400821

  日期：2015.2.9

  AbstractPolystyrene‐supported 9‐amino‐9‐deoxy‐epi‐quinine was synthesized through co‐polymerization of an ad hoc‐designed chiral monomer with divinylbenzene, in the presence of azobis(isobutyronitile) (AIBN) as radical initiator and toluene and 1‐dodecanol as porogenic solvents. The heterogenized catalyst efficiently promoted the reaction of isobutyric aldehyde with β‐nitrostyrene, in very high yield and enantioselectivity, comparable or even higher than that of the homogeneous counterpart (up to 95% ee). The recyclability of the catalyst, its general applicability and its successful application to other reactions was also demonstrated. Finally, for the first time, a 9‐amino‐epi‐quinine derivative was employed to perform an enantioselective Michael reaction under continuous‐flow conditions; by using a home‐made, packed‐bed catalytic reactor, the aldehyde addition to nitrostyrene was successfully realized in flow mode, leading to the product in up to 93% ee.magnified image
• Synthesis of highly decorated chiral 2-nitro-cyclohexane carboxylic esters through microwave-assisted organocatalyzed cascade reactions
  作者：Elisabetta Massolo、Maurizio Benaglia、Davide Parravicini、Davide Brenna、Rita Annunziata

  DOI：10.1016/j.tetlet.2014.10.073

  日期：2014.12

  Starting from (E)-beta-substituted-beta-nitroacrylates and alpha,beta-unsaturated ketones, a stereoselective organo-catalyzed one-pot methodology allowed to synthesize highly decorated chiral 2-nitro-cyclohexane carboxylic esters. The reaction is promoted by Cinchona alkaloid-derived primary amines in the presence of an acidic co-catalyst and affords two diastereoisomers, in good yields and high enantiomeric excess (often higher than 90% ee). By replacing conventional heating with microwave irradiation, cleaner reactions in shortened times (from 48 h to 30 min) were obtained, with improved dr (80:20) and high ee (up to 94%). The application of microwave technology to this organocatalytic methodology allowed also employing Cl substituted enones, leading to cyclohexanones with four contiguous stereocenters in two isomers only, and up to 99% enantioselectivity. (C) 2014 Elsevier Ltd. All rights reserved.