(S)-ethyl 3-nitro-2-phenylpropanoate | 1070238-04-8

• 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: (S)-ethyl 3-nitro-2-phenylpropanoate
• 英文别名: ethyl 3-nitro-2-phenylpropanoate；ethyl (2S)-3-nitro-2-phenylpropanoate
• CAS: 1070238-04-8
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: HPSXSPNCILFZKH-SNVBAGLBSA-N

物化性质

• 沸点：
  342.4±35.0 °C(Predicted)
• 密度：
  1.182±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-ethyl 3-nitro-2-phenylpropanoate 在 sodium tetrahydroborate 、 nickel (II) chloride hexahydrate 作用下， 以 乙醇 为溶剂， 反应 0.25h， 以90%的产率得到ethyl 3-amino-2-phenylpropanoate
  参考文献：
  名称：

  Organocatalytic Asymmetric Transferhydrogenation of β-Nitroacrylates: Accessing β²-Amino Acids

  摘要：

  We describe a highly efficient and enantioselective Hantzsch ester mediated conjugate reduction of beta-nitroacrylates that is catalyzed by a Jacobsen thiourea catalyst as a key step in a new route to optically active beta2-amino acids.

  DOI：

  10.1021/ja8069852
• 作为产物：
  描述：

  苯甲酰甲酸乙酯 在 [Ir(1,5-cyclooctadiene)((tBu)C7H10NOP(tBu))] tetrakis(3,5-bis(trifluoromethyl)phenyl)borate 、 氢气 、 甲基磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 20.0~80.0 ℃ 、5.07 MPa 条件下， 反应 48.0h， 生成 (S)-ethyl 3-nitro-2-phenylpropanoate
  参考文献：
  名称：

  First Iridium-Catalyzed Highly Enantioselective Hydrogenation of β-Nitroacrylates

  摘要：

  The first highly chemo- and enantioselective hydrogenation of beta-nitroacrylates was accomplished with an iridium catalyst (Ir-4) with yields and enantioselectivities of up to 96% and 98% ee, respectively. The resulting alpha chiral beta-nitro propionates are attractive building blocks for the synthesis of chiral beta(2)-amino acids, which are the core scaffolds of bioactive natural products, pharmaceuticals, and beta-peptides.

  DOI：

  10.1021/acs.orglett.5b01758

文献信息

• Readily available hydrogen bond catalysts for the asymmetric transfer hydrogenation of nitroolefins
  作者：Jakob F. Schneider、Markus B. Lauber、Vanessa Muhr、Domenic Kratzer、Jan Paradies

  DOI：10.1039/c1ob05059a

  日期：——

  focuses on readily accessible thiourea hydrogen bond catalysts derived from amino acids, whose steric and electronic features are modulated by their degree of substitution at the carbinol carbon center. These catalysts were applied in the asymmetric transfer hydrogenation of nitroolefins furnishing the chiral products in up to 99% yield and 86% enantiomeric excess. The proposed catalyst's mode of action

  本文着重于易于访问的内容 硫脲衍生自氨基酸的氢键催化剂，其位阻和电子特征受其在甲醇碳中心的取代度的调节。这些催化剂被用于硝基烯烃的不对称转移氢化，从而以高达99％的收率和86％的对映体过量提供手性产物。所提出的催化剂的作用方式得到机理研究的支持。
• Synthesis of Quaternary-Carbon-Containing β^2,2-Amino Acids by the Rh^I-Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates
  作者：Jo-Hsuan Fang、Jia-Hong Jian、Hao-Ching Chang、Ting-Shen Kuo、Way-Zen Lee、Ping-Yu Wu、Hsyueh-Liang Wu

  DOI：10.1002/chem.201604120

  日期：2017.2.3

  An enantioselective RhI‐catalyzed conjugate addition reaction of α‐substituted β‐nitroacrylates with various arylboronic acids by using chiral RhI diene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary‐carbon‐containing α,α‐disubstituted β‐nitropropionate products

  首次描述了使用手性Rh I二烯催化剂对α-取代的β-硝基丙烯酸酯与各种芳基硼酸的对映选择性Rh I催化的共轭加成反应。加成反应在温和的条件下在一系列常见的有机溶剂和添加剂中进行，从而以高达63％的收率和99％ee的产率提供相应的含季碳的α，α-二取代的β-硝基丙酸酯产品。（E）-或（Z）-β-硝基丙烯酸酯的反应提供了相同的产物对映异构体，并且可以耐受一系列的酯和芳基。为了证明该方法的实用性，乙基（R苯基）-1,1-二甲基-1-苯基-3- nitropropionate，制备本文中，转化成非蛋白原β 2,2 -氨基磺酸，（- [R）-2-（氨基甲基）-2-苯基丙酸和β ，2-内酰胺，（R）-3-甲基-3-苯基氮杂环丁烷-2-one。此外，三肽，其包括（comprised）升-苯丙氨酸，升-丙氨酸，β和2,2 -氨基酸7，还合成。
• A General Catalytic Enantioselective Transfer Hydrogenation Reaction of β,β-Disubstituted Nitroalkenes Promoted by a Simple Organocatalyst
  作者：Luca Bernardi、Mariafrancesca Fochi

  DOI：10.3390/molecules21081000

  日期：——

  encompassing various nitroalkene classes; (ii) Hantzsch esters as convenient (on a preparative scale) hydrogen surrogates; (iii) a simple and commercially available thiourea as catalyst; (iv) user-friendly procedures. Overall, the proposed protocol gives a practical dimension to the catalytic enantioselective reduction of β,β-disubstituted nitroalkenes, offering a useful and general platform for the preparation

  鉴于其合成相关性，β，β-二取代硝基烯烃的催化对映选择性还原受到了广泛关注。已经开发了几种生物，金属和有机催化方法，但是这些方法通常适用于单类硝基烯烃底物。在本文中，我们介绍了我们以前在此转化方面的工作，该工作以新的公开内容和机械的见解得以实施，从而产生了一种非常通用的硝基烯烃还原方案。所提出的方法的特点是：（i）涵盖各种硝基烯烃类的范围非常广；（ii）方便的（制备规模的）氢代酸盐的汉茨酯；（iii）一种简单的可商购的硫脲作为催化剂；（iv）人性化的程序。总体，所提出的方案为β，β-二取代的硝基链烯烃的催化对映选择性还原提供了实用的方法，为制备高度对映体富集的β-位立体异构中心的硝基链烷提供了有用的通用平台。提出并讨论了从控制动力学实验出发，结合文献数据得出的过渡态模型。该模型说明并证明了观察到的实验结果。
• Pd-catalyzed asymmetric conjugate addition of arylboronic acids to 2-nitroacrylates: a facile route to β2-homophenylglycines
  作者：Andreas Petri、Oliver Seidelmann、Uwe Eilitz、Frank Leßmann、Stefan Reißmann、Volkmar Wendisch、Andrey Gutnov

  DOI：10.1016/j.tetlet.2013.11.015

  日期：2014.1

  Asymmetric conjugate addition of arylboronic acids to 2-nitroacrylamide in the presence of cationic palladium-Chiraphos complex proceeds with high yield and enantioselectivity (73-89% ee) using as low as 0.05-0.25 mol % of the catalyst. The adducts can be smoothly transformed into the corresponding beta(2)-homophenylglycines in two simple steps. (C) 2013 Elsevier Ltd. All rights reserved.
• First Iridium-Catalyzed Highly Enantioselective Hydrogenation of β-Nitroacrylates
  作者：Shengkun Li、Taifeng Xiao、Dangdang Li、Xumu Zhang

  DOI：10.1021/acs.orglett.5b01758

  日期：2015.8.7

  The first highly chemo- and enantioselective hydrogenation of beta-nitroacrylates was accomplished with an iridium catalyst (Ir-4) with yields and enantioselectivities of up to 96% and 98% ee, respectively. The resulting alpha chiral beta-nitro propionates are attractive building blocks for the synthesis of chiral beta(2)-amino acids, which are the core scaffolds of bioactive natural products, pharmaceuticals, and beta-peptides.