(-)-methyl 2-carbomethoxy-4-nitro-3-(4-fluorophenyl)butyrate | 771562-78-8

• 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: (-)-methyl 2-carbomethoxy-4-nitro-3-(4-fluorophenyl)butyrate
• 英文别名: (R)-methyl 2-carbomethoxy-4-nitro-3-(4-fluorophenyl)butyrate；dimethyl [(1R)-1-(4-fluorophenyl)-2-nitroethyl]propanedioate；dimethyl (R)-2-(1-(4-fluorophenyl)-2-nitroethyl)malonate；dimethyl 2-[(1R)-1-(4-fluorophenyl)-2-nitroethyl]propanedioate
• CAS: 771562-78-8
• 化学式: C₁₃H₁₄FNO₆
• 分子量: 299.256
• InChiKey: SNAYWJCAGLBWEU-JTQLQIEISA-N

物化性质

• 熔点：
  46-49 °C
• 沸点：
  409.5±45.0 °C(Predicted)
• 密度：
  1.301±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  98.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 苄胺 、 (-)-methyl 2-carbomethoxy-4-nitro-3-(4-fluorophenyl)butyrate 以 甲醇 为溶剂， 反应 16.0h， 以68%的产率得到methyl (3S,4R,5R)-1-benzyl-4-(4-fluorophenyl)-5-nitro-2-oxopiperidine-3-carboxylate
  参考文献：
  名称：

  Organocatalytic Asymmetric Total Synthesis of (R)-Rolipram and Formal Synthesis of (3S,4R)-Paroxetine

  摘要：

  An efficient enantioselective total synthesis of (R)-rolipram and an efficient enantioselective formal synthesis of (3S,4R)-paroxetine has been achieved using the highly enantioselective Michael addition of malonate nucleophiles as key steps in both cases.

  DOI：

  10.1021/ol800108u
• 作为产物：
  描述：

  1-氟-3-(2-硝基乙烯基)苯 、 丙二酸二甲酯 在 萘 、 4-[(S)-[3,5-bis[[(S)-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-hydroxyquinolin-4-yl)methoxy]methyl]phenyl]methoxy-[(2R,4S,5R)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]methyl]quinolin-6-ol 作用下， 以 四氢呋喃 为溶剂， 反应 72.0h， 以81%的产率得到(-)-methyl 2-carbomethoxy-4-nitro-3-(4-fluorophenyl)butyrate
  参考文献：
  名称：

  高效且高效的不对称迈克尔加成反应：开发出高对映选择性奎尼丁基有机催化剂，可通过纳滤实现均质回收

  摘要：

  相对较高的成本和较低的除了所需的高催化负载量（通常为1至30 mol％）外，手性有机催化剂的可用性对经济性不对称有机催化方法的工业发展提出了普遍的挑战。可以通过回收有机催化剂来解决这一挑战。在这项工作中，评估了基于金鸡纳生物碱奎尼丁的一类有机催化剂对活性药物成分（API）的对映选择性合成步骤的潜力。通过聚烷基化扩大有机催化剂使有机催化剂更易于通过有机溶剂纳滤（OSN）膜进行再循环。每种有机催化剂候选物的分子大小，分子电荷和形成氢键的能力都是决定催化剂的膜保留率的重要因素。通过OSN。另外，与未扩大的催化剂相比，对于扩大的催化剂，观察到催化性能的显着改善，对于所有催化的不对称迈克尔加成物，获得的对映选择性> 92％ee。最后，实施了两阶段的膜工艺以提高催化剂回收工艺的生产率，从而使回收工艺所需的溶剂减少了96％。

  DOI：

  10.1039/c2gc36407g

文献信息

• Catalytic Enantioselective Michael Addition of 1,3-Dicarbonyl Compounds to Nitroalkenes Catalyzed by Well-Defined Chiral Ru Amido Complexes
  作者：Masahito Watanabe、Ayako Ikagawa、Hui Wang、Kunihiko Murata、Takao Ikariya

  DOI：10.1021/ja046296g

  日期：2004.9.1

  Well-defined chiral Ru amido complexes promoted asymmetric Michael addition of 1,3-dicarbonyl compounds including malonates, beta-keto esters, and 1,3-diketones to nitroalkenes to give the corresponding adducts with excellent ees and in excellent yields.

  明确定义的手性 Ru 酰胺配合物促进 1,3-二羰基化合物（包括丙二酸酯、β-酮酯和 1,3-二酮）与硝基烯烃的不对称迈克尔加成反应，得到相应的加合物，具有优异的 ees 和优异的产率。
• Biscinchona alkaloids as highly efficient bifunctional organocatalysts for the asymmetric conjugate addition of malonates to nitroalkenes at ambient temperature
  作者：Fei Li、Ying-Zi Li、Zhen-Shan Jia、Ming-Hua Xu、Ping Tian、Guo-Qiang Lin

  DOI：10.1016/j.tet.2011.08.070

  日期：2011.12

  The novel bifunctional bisalkaloids have been developed as highly efficient catalysts for the asymmetric conjugate addition of 1,3-dicarbonyl compounds to nitroalkenes with low catalyst loading (1 mol %) at ambient temperature, providing the products with excellent enantioselectivities (up to 97% ee). Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.
• Calixarene-derived chiral tertiary amine–thiourea organocatalyzed asymmetric Michael additions of acetyl acetone and dimethyl malonate to nitroolefins
  作者：Mustafa Durmaz、Aysun Tataroglu、Horu Yilmaz、Abdulkadir Sirit

  DOI：10.1016/j.tetasy.2016.01.004

  日期：2016.2

  Novel bifunctional chiral thiourea-tertiary amines bearing a calix[4]arene scaffold were synthesized and applied in catalytic asymmetric Michael addition of acetyl acetone and dimethyl malonate to nitroolefins. The corresponding adducts were obtained in excellent yields (up to 99%) and with high enantioselectivities (up to 94% ee). (C) 2016 Elsevier Ltd. All rights reserved.
• Highly Selective Cascade Couplings for the Syntheses of Functionalized Piperidinones and Bispidines
  作者：Feng Xu、Edward Corley、Jerry A. Murry、David M. Tschaen

  DOI：10.1021/ol070909n

  日期：2007.7.1

  Efficient cascade couplings to synthesize functionalized piperidinones 1 and bispidines 2 and 3 have been developed. Simple modifications to the reaction conditions allow for the highly controlled and selective formation of each compound. In addition, the cis isomer of 1 can be selectively obtained under acidic conditions, while the preparation of the corresponding trans isomer can also be readily realized through a base-catalyzed, dynamic crystallization-driven process.