ethyl 2-hydroxy-4-(4-methylphenyl)-3-nitrobut-3(E)-enoate | 1262022-92-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: ethyl 2-hydroxy-4-(4-methylphenyl)-3-nitrobut-3(E)-enoate
• CAS: 1262022-92-3
• 化学式: C₁₃H₁₅NO₅
• 分子量: 265.266
• InChiKey: FGFWIMSAVIAFQN-DHZHZOJOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.54
• 重原子数：
  19.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  89.67
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  ethyl 2-hydroxy-4-(4-methylphenyl)-3-nitrobut-3(E)-enoate 在 对硝基苯酚 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.83h， 生成 (2R,3S,4R)-ethyl-5-methyl-3-nitro-1-phenyl-4-(p-tolyl)-1,2,3,4-tetrahydropyridine-2-carboxylate
  参考文献：
  名称：

  二氢恶嗪N-氧化物中间体作为功能性硝基烯丙基胺与醛的有机催化动力学拆分中的静止状态

  摘要：

  通过手性α，α- 1-二苯基脯氨醇甲硅烷基醚助剂，通过分离二氢恶嗪N-氧化物中间体，建立了硝基烯丙基胺的动力学拆分。进一步水解静置态可提供高化学产率和高至优异的立体选择性（高达> 20：1 dr和98％ee）的四氢吡啶。通过计算探索了二氢恶嗪中立体选择性质子化的详细机理解释。另外，分离了醛的α-卤化中可能的中间体（被烯胺掩盖），以提供结晶学证据。

  DOI：

  10.1021/acs.orglett.6b00493
• 作为产物：
  描述：

  对甲基苯甲醛 在 咪唑 、 sodium hydroxide 作用下， 以 甲醇 、 氯仿 为溶剂， 生成 ethyl 2-hydroxy-4-(4-methylphenyl)-3-nitrobut-3(E)-enoate
  参考文献：
  名称：

  二氢恶嗪N-氧化物中间体作为功能性硝基烯丙基胺与醛的有机催化动力学拆分中的静止状态

  摘要：

  通过手性α，α- 1-二苯基脯氨醇甲硅烷基醚助剂，通过分离二氢恶嗪N-氧化物中间体，建立了硝基烯丙基胺的动力学拆分。进一步水解静置态可提供高化学产率和高至优异的立体选择性（高达> 20：1 dr和98％ee）的四氢吡啶。通过计算探索了二氢恶嗪中立体选择性质子化的详细机理解释。另外，分离了醛的α-卤化中可能的中间体（被烯胺掩盖），以提供结晶学证据。

  DOI：

  10.1021/acs.orglett.6b00493

文献信息

• Organocatalytic Kinetic Resolution of Racemic Secondary Nitroallylic Alcohols Combined with Simultaneous Desymmetrization of Prochiral Cyclic Anhydrides
  作者：Suparna Roy、Kan-Fu Chen、Ramani Gurubrahamam、Kwunmin Chen

  DOI：10.1021/jo501882q

  日期：2014.10.3

  This study describes an organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols (2) combined with simultaneous desymmetrization of prochiral cyclic anhydrides (1). The experimental results revealed that enantioselective alcoholysis of 3-substituted glutaric anhydrides afforded hemiesters (3) with high levels of enantioselectivities (up to 99% ee) in the presence of cinchonidine-derived thiourea catalyst (IV). The highly optical enrichment (up to 95% ee) of (S)-nitroallylic alcohols (2) was recovered.
• An efficient Morita–Baylis–Hillman reaction for the synthesis of multifunctional 2-hydroxy-3-nitrobut-3-enoate derivatives
  作者：Hsuan-Hao Kuan、Raju Jannapu Reddy、Kwunmin Chen

  DOI：10.1016/j.tet.2010.10.061

  日期：2010.12

  An efficient thiourea promoted MBH reaction of various conjugated nitroalkenes with ethyl glyoxylate was developed. The desired multifunctional products, 2-hydroxy-3-nitro-4-aryl/alkylbut-3-enoate derivatives were obtained in good to high chemical yields (56-92%) with DMAP (20 mol%) under solvent-free conditions or imidazole (100 mol%) in the presence of water. (C) 2010 Elsevier Ltd. All rights reserved.
• Control of Five Contiguous Stereogenic Centers in an Organocatalytic Kinetic Resolution via Michael/Acetalization Sequence: Synthesis of Fully Substituted Tetrahydropyranols
  作者：Ramani Gurubrahamam、You-Song Cheng、Kwunmin Chen

  DOI：10.1021/ol5033656

  日期：2015.2.6

  An organocatalytic kinetic resolution of racemic secondary nitroallylic alcohols via Michael/acetalization sequence to give fully substituted tetrahydropyranols is described. The process affords the products with high to excellent stereoselectivities (up to 19.9:1.5:1 dr and 98% ee). The highly enantioenriched, less reactive (S)-nitroallylic alcohols 3 were isolated with good to high chemical yields (30-44%). The synthetic application of the resolved substrate is shown toward the synthesis of enantioenriched (+)-(2S,3R)-3-amino-2-hydroxy-4-phenylbutyric acid.
• Dihydrooxazine <i>N</i>-Oxide Intermediates as Resting States in Organocatalytic Kinetic Resolution of Functionalized Nitroallylic Amines with Aldehydes
  作者：Ramani Gurubrahamam、Yan ming Chen、Wan-Yun Huang、Yu-Te Chan、Hsiang-Kai Chang、Ming-Kang Tsai、Kwunmin Chen

  DOI：10.1021/acs.orglett.6b00493

  日期：2016.7.1

  stereoselectivities (up to >20:1 dr and 98% ee). A detailed mechanistic explanation for stereoselective protonation in the dihydrooxazine was probed computationally. In addition, the probable intermediates in α-halogenation of aldehydes (masked with enamines) were isolated to provide crystallographic evidence.

  通过手性α，α- 1-二苯基脯氨醇甲硅烷基醚助剂，通过分离二氢恶嗪N-氧化物中间体，建立了硝基烯丙基胺的动力学拆分。进一步水解静置态可提供高化学产率和高至优异的立体选择性（高达> 20：1 dr和98％ee）的四氢吡啶。通过计算探索了二氢恶嗪中立体选择性质子化的详细机理解释。另外，分离了醛的α-卤化中可能的中间体（被烯胺掩盖），以提供结晶学证据。