methyl 3-(methylphenylamino)-2-propenoate | 7542-92-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: methyl 3-(methylphenylamino)-2-propenoate
• 英文别名: Methyl beta-[N-methylanilino]acrylate；methyl (E)-3-(N-methylanilino)prop-2-enoate
• CAS: 7542-92-9
• 化学式: C₁₁H₁₃NO₂
• 分子量: 191.23
• InChiKey: UOOQICQDTDRLNT-CMDGGOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 3-(methylphenylamino)-2-propenoate 在 disodium hydrogenphosphate 、 氟硼酸钠 、 fac-tris(2-phenylpyridinato-N,C2')iridium(III) 、 sodium ascorbate 、 sodium iodide 作用下， 以 丙酮 、 乙腈 为溶剂， 反应 1.0h， 生成 diethyl 2-((2R,3R)-2-(methoxycarbonyl)-5-methyl-3-(methyl(phenyl)amino)-4-(phenylsulfonyl)-2,3-dihydrofuran-2-yl)malonate
  参考文献：
  名称：

  基于双氧化[3 + 3]环加成反应的二氢吡喃并[4,3-b]吲哚的电合成。

  摘要：

  氧化性[3 + 3]环加成反应为六元环形成提供了一条有效途径。该方法是基于吲哚/烯胺与活性亚甲基化合物的电化学氧化偶联，然后串联6π-电环化反应生成二氢吡喃并[4,3- b ]吲哚和2,3-二氢呋喃而实现的。阳极氧化产生的自由基与自由基从O 2产生的自由基之间的自由基交叉偶联为合成结构复杂的杂环提供了温和的反应条件。

  DOI：

  10.1002/anie.202003364
• 作为产物：
  描述：

  4-(N-甲基苯胺基)-4-氧代丁酸 在 rhodium(II) acetate dimer 、 三乙胺 、 氯甲酸甲酯 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 methyl 3-(methylphenylamino)-2-propenoate
  参考文献：
  名称：

  A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process

  摘要：

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.

  DOI：

  10.1021/jo952078h

文献信息

• Palladium-Catalyzed C-S Bond Formation of Stable Enamines with Arene/Alkanethiols: Highly Regioselective Synthesis of β-Amino Sulfides
  作者：Yaojia Jiang、Gaohui Liang、Cong Zhang、Teck-Peng Loh

  DOI：10.1002/ejoc.201600588

  日期：2016.7

  A direct and regiocontrolled thiolation method to access β-amino sulfides through the palladium-catalyzed C(sp2)–H functionalization of stable enamines was described. The reaction was realized under mild conditions by adding an external phosphine ligand to prevent poisoning of the palladium catalyst by the sulfuric reagents. A possible mechanism was proposed according to the obtained results. The DFT

  描述了一种通过钯催化的稳定烯胺的 C(sp2)-H 官能化获得 β-氨基硫化物的直接和区域控制的硫醇化方法。该反应在温和条件下通过添加外部膦配体来实现，以防止钯催化剂被硫酸试剂中毒。根据所得结果提出了一种可能的机制。DFT 计算结果与实验数据一致，给出了 β-氨基硫化物的 E 异构体。该反应也以克规模进行，并显示出在有机合成中的潜在应用。
• Efficient synthesis of β-enaminoesters via highly stereoselective Reformatsky reaction with disubstituted formamides as novel electrophiles
  作者：Yi-Yin Ke、Yu-Jin Li、Jian-Hong Jia、Wei-Jian Sheng、Liang Han、Jian-Rong Gao

  DOI：10.1016/j.tetlet.2009.01.003

  日期：2009.4

  An efficient synthesis of various β-enaminoesters has been achieved via Reformatsky reaction with disubstituted formamides as novel electrophiles. The exclusive β-enaminoester E-isomers were obtained in 60–72% yield.

  通过与二取代甲酰胺作为新型亲电试剂的Reformatsky反应，已实现了各种β-烯氨基酯的有效合成。以60–72％的产率获得了独家的β-烯氨基酯E-异构体。
• Palladium-Catalyzed Oxidative Amination of Activated Olefins with N-Alkyl Anilines for Synthesis of Tertiary (E)-Enamines
  作者：Mi-Na Zhao、Xiao-Li Lian、Zhi-Hui Ren、Yao-Yu Wang、Zheng-Hui Guan

  DOI：10.1039/c4ra11543k

  日期：——

  An efficient palladium-catalyzed oxidative amination of olefins with secondary anilines for the synthesis of tertiary (E)-enamines has been developed. Trimethylacetic acid (PivOH) played an important role in the reaction. This protocol tolerates a range of functional groups and is a reliable method for direct synthesis of tertiary (E)-enamines in high yields under mild conditions.

  已经开发了用于仲（E）-烯胺的合成的具有仲苯胺的烯烃的钯的有效催化氧化胺化。三甲基乙酸（PivOH）在反应中起重要作用。该方案可耐受一定范围的官能团，是在温和条件下以高收率直接合成叔（E）-烯胺的可靠方法。
• Stereoselective Chlorination and Bromination of Enamides and Enamines via an Electrostatic Attraction Effect Using (1,1-Diacetoxyiodo)benzene and a Halide Source
  作者：Linlin Xing、Chunbao Li

  DOI：10.1021/acs.joc.5b01603

  日期：2015.10.16

  structure of the intermediates, the conformations of which are controlled by the electrostatic attractions between the positively charged nitrogen atoms and the oxygen atoms of the carbonyl group. This type of electrostatic effect has never been reported in olefin halogenations. For this reason, the three-membered bromonium ion is only a minor intermediate in the enamine bromination pathway. These methods

  使用NiCl 2 ·6H 2 O或四丁基铵可以实现（E）-烯胺和（Z）-酰胺直接氯化和溴化为相应的（Z）-构型的α-氯烯胺，α-溴烯胺和α-氯烯酰胺。溴化物为卤化物源，（1,1-二乙酰氧基碘）苯为氧化剂。仅产生（Z-构型可以归因于中间体的结构，其构象由带正电荷的氮原子和羰基的氧原子之间的静电引力控制。在烯烃卤化中从未报道过这种类型的静电作用。因此，三元溴离子只是烯胺溴化途径中的次要中间体。这些方法打开了制备α-氯烯胺和α-氯烯酰胺的途径，而这是目前使用的方法无法获得的。
• Huisgen,R. et al., Chemische Berichte, 1966, vol. 99, p. 2526 - 2545
  作者：Huisgen,R. et al.

  DOI：——

  日期：——