ethyl 2-acetoxy-4-(3-methoxyphenyl)-3-nitrobut-3-enoate | 1394173-93-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: ethyl 2-acetoxy-4-(3-methoxyphenyl)-3-nitrobut-3-enoate
• CAS: 1394173-93-3
• 化学式: C₁₅H₁₇NO₇
• 分子量: 323.302
• InChiKey: RZPFQYTVDYTYKM-UHFFFAOYSA-N

物化性质

• 沸点：
  478.5±45.0 °C(predicted)
• 密度：
  1.258±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.81
• 重原子数：
  23.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  104.97
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (4-methoxy-4-oxobut-2-enyl)-dimethylsulfanium;bromide 、 ethyl 2-acetoxy-4-(3-methoxyphenyl)-3-nitrobut-3-enoate 在 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 0.75h， 以52%的产率得到5-ethyl 2-methyl 3′-methoxy-[1,1′-biphenyl]-2,5-dicarboxylate
  参考文献：
  名称：

  （3 + 3）硝基烯丙基乙酸盐与稳定的硫磺盐合成2-对苯二甲酸对苯二甲酸酯的合成

  摘要：

  已经开发了一种新颖的（3 + 3）环空方法，用于从硝基烯丙基乙酸酯和稳定的硫酰化物合成对苯二甲酸2-芳基酯。的2-芳基对苯二甲酸酯，其也是联芳基带有对苯二甲酸乙二醇酯部分，通过反应器的级联形成诸如γ-选择性小号Ñ 2'反应，γ-选择性分子内迈克尔加成和两个抵销在Cs的存在2室温下CH 3 CN中的CO 3。该产品是法尼基转移酶抑制剂的正式前体，也是聚合物化学中的潜在单体。

  DOI：

  10.1021/acs.joc.8b00917

文献信息

• Kinetic Resolution of Activated Nitroallylic Acetates with Aldehydes and Ketones through a Conjugate Addition-Elimination SN2′ Process
  作者：Raju Jannapu Reddy、Pei-Hsun Lee、Dhananjay R. Magar、Jung-Hsuan Chen、Kwunmin Chen

  DOI：10.1002/ejoc.201101162

  日期：2012.1

  A unique organocatalytic kinetic resolution (KR) of nitroallylic acetates has been developed. A variety of racemic nitroallylic acetates (1a–n) were resolved with chiral enamines formed in situ from the reaction of aldehydes and ketones with organocatalyst 2b (2.5 mol-%) and 14c (20 mol-%), respectively, through an interesting SN2′ reaction. The densely functionalized products 3–5 were obtained with

  已开发出硝基烯丙基乙酸酯的独特有机催化动力学拆分 (KR)。各种外消旋硝基烯丙基乙酸酯 (1a-n) 分别由醛和酮与有机催化剂 2b (2.5 mol-%) 和 14c (20 mol-%) 反应形成的手性烯胺通过有趣的 SN2 分离' 反应。以高到高的立体选择性（高达> 99:1 dr 和> 99 % ee）以良好到高的化学产率获得了密集功能化的产品 3-5。未反应的起始底物 1a-n 以良好到高的光学纯度（高达 98% ee）回收。动力学拆分的范围和通用性被扩展到包括各种醛和酮作为供体来源的各种硝基烯丙基乙酸酯。确定官能化产物和未反应底物的绝对立体化学。当 (S)-香茅醛在 2b 存在下用 rac-1a 处理得到 12 作为单一非对映异构体，进一步环化得到具有优异立体选择性的四取代环己烷衍生物 13 时，证明了合成应用。提出了过渡态模型来解释 KR 过程中的立体化学偏差。
• Silica gel-Mediated Friedel-Crafts Reaction of Indoles with Functionalized Nitroallylic Acetates via an SN1 Process
  作者：Ching-Yin Ho、Suparna Roy、Yan-Ming Chen、Kwunmin Chen

  DOI：10.1002/jccs.201100643

  日期：2012.8

  An environmentally friendly Friedel‐Crafts reaction was demonstrated between indoles and functionalized nitroallylic acetates in the presence of silica gel, providing the corresponding C‐3‐selective regioisomers in good to high overall chemical yields (70‐93%).

  在硅胶存在下，吲哚和官能化的硝基烯丙基乙酸酯之间发生了环保的Friedel-Crafts反应，证明了相应的C-3选择区域异构体具有良好的化学总收率（70-93％）。
• Synthesis of Densely Substituted Sulfonylfurans and Dihydrofurans via Cascade Reactions of α-Functionalized Nitroalkenes with β-Ketosulfones
  作者：Vaijinath Mane、Sudheesh T. Sivanandan、Rafael G. Santana、Adilson Beatriz、Eufrânio N. da Silva Júnior、Irishi N. N. Namboothiri

  DOI：10.1021/acs.joc.0c00606

  日期：2020.7.17

  substrate scope. Application of these products has been demonstrated by the synthesis of pyrroles and pyrazoles in good yields. The reaction of β-ketosulfones with nitroallylic acetates yields tetrasubstituted sulfonyl furans through a cascade SN2′-intramolecular Michael reaction, followed by aromatization. The gram-scale synthesis of a representative example of sulfonylfurans was carried out to demonstrate

  β-酮砜与不同的α-官能化的硝基烯烃反应可得到取代的磺酰基呋喃和二氢呋喃。此外，β-酮砜通过级联的迈克尔加成环化方案与α-溴硝基烯烃和α-肼基硝基烯烃反应，分别得到带有关键磺酰基的硝基二氢呋喃和肼基二氢呋喃，具有优异的收率，具有广泛的底物范围。这些产品的应用已通过高产率合成吡咯和吡唑得到了证明。β-酮砜与硝基烯丙基乙酸酯的反应通过级联S N生成四取代的磺酰呋喃2'-分子内迈克尔反应，然后进行芳构化。进行了克规模的磺酰呋喃代表性实例的合成，以证明该方法的合成效率。
• An Unusual Route to Synthesize Indolizines through a Domino S _N 2/Michael Addition Reaction Between 2‐Mercaptopyridine and Nitroallylic Acetates
  作者：Suparna Roy

  DOI：10.1002/ejoc.201801426

  日期：2019.1.31

  An unusual reaction between 2‐mercaptopyridine and nitroallylic acetates has been demonstrated. The reaction is initiated by a domino sequence including an SN2 reaction at tertiary center followed by a Michael addition and removal of sulfur moiety to deliver substituted indolizines.

  已证明2-巯基吡啶与乙酸烯丙酯之间存在异常反应。该反应由在三级中心包括S N 2反应的多米诺序列引发，然后进行迈克尔加成并去除硫部分以递送取代的吲哚嗪。
• The combination of domino process and kinetic resolution: organocatalytic synthesis of functionalised cyclopentenes by sequential SN2′-Michael reaction
  作者：Lun Fu Yeh、Shaik Anwar、Kwunmin Chen

  DOI：10.1016/j.tet.2012.06.085

  日期：2012.9

  An interesting combination of organocatalytic cascade reaction and kinetic resolution was developed for the synthesis of functionalised cyclopentenes by sequential S(N)2'-Michael process. Treatment of the racemic nitroallylic acetates with glutaraldehyde in the presence of diphenylprolinol silyl ether to give tetrasubstituted cyclopentenes with high to excellent stereoselectivities (up to 96% ee and 12:1 dr). The less reactive enantiomeric substrates were generally recovered with good to excellent optical purities (up to 99% ee). (C) 2012 Published by Elsevier Ltd.