(Z)-methyl 2-acetamido-3-(o-tolyl)acrylate | 889863-27-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (Z)-methyl 2-acetamido-3-(o-tolyl)acrylate
• 英文别名: methyl (Z)-2-acetamido-3-(o-tolyl)acrylate；methyl (Z)-2-acetamido-3-(2-methylphenyl)prop-2-enoate
• CAS: 889863-27-8
• 化学式: C₁₃H₁₅NO₃
• 分子量: 233.267
• InChiKey: MPGIUDWJFIZEGA-WQLSENKSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  55.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-methyl 2-acetamido-3-(o-tolyl)acrylate 在 [Rh((R,R)-DIPAMP)(COD)]BF₄ 盐酸 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 18.0h， 生成 2-methyl-L-phenylalanine hydrochloride
  参考文献：
  名称：

  Enantioselective Synthesis of a Phenylalanine Library Containing Alkyl Groups on the Aromatic Moiety: Confirmation of Stereostructure by X-Ray Analysis

  摘要：

  通过不对称氢化乙酰氨基丙烯酸酯衍生物，立体选择性地合成了六种含有2′-甲基-、2′,6′-二甲基-、2′-乙基-6′-甲基-、2′-异丙基-6′-甲基-、2′,4′,6′-三甲基-和3′,5′-二甲基-L-苯丙氨酸的苯丙氨酸类似物。酶解和X射线分析证实了所获得的苯丙氨酸衍生物的L构型。

  DOI：

  10.1248/cpb.54.873
• 作为产物：
  描述：

  2-碘代甲苯 、 2-乙酰胺基丙烯酸甲酯 在 palladium diacetate 、 三乙胺 、 三(邻甲基苯基)磷 作用下， 以 乙腈 为溶剂， 反应 10.0h， 以75%的产率得到(Z)-methyl 2-acetamido-3-(o-tolyl)acrylate
  参考文献：
  名称：

  Enantioselective Synthesis of a Phenylalanine Library Containing Alkyl Groups on the Aromatic Moiety: Confirmation of Stereostructure by X-Ray Analysis

  摘要：

  通过不对称氢化乙酰氨基丙烯酸酯衍生物，立体选择性地合成了六种含有2′-甲基-、2′,6′-二甲基-、2′-乙基-6′-甲基-、2′-异丙基-6′-甲基-、2′,4′,6′-三甲基-和3′,5′-二甲基-L-苯丙氨酸的苯丙氨酸类似物。酶解和X射线分析证实了所获得的苯丙氨酸衍生物的L构型。

  DOI：

  10.1248/cpb.54.873

文献信息

• Ni(<scp>ii</scp>)-Catalyzed vinylic C–H functionalization of 2-acetamido-3-arylacrylates to access isotetronic acids
  作者：Biswajit Roy、Eshani Das、Avijit Roy、Dipakranjan Mal

  DOI：10.1039/d0ob00557f

  日期：——

  reaction for the synthesis of 4-aryl-substituted isotetronic acids from 2-acetamido-3-arylacrylates via vinylic C-H functionalization is reported. The reaction proceeds through heteroatom guided electrophilic insertion of nickel to the vinylic double bond followed by annulation with dibromomethane. This unconventional route features cascade steps, sole product formation, multiple functional group tolerance

  报道了通过乙烯基CH官能团由2-乙酰氨基-3-芳基丙烯酸酯合成4-芳基取代的等渗酸的无配体Ni（ii）催化的级联环化反应。该反应通过镍的杂原子引导的亲电子插入到乙烯基双键中，然后用二溴甲烷环化而进行。该非常规途径具有级联步骤，单一产物形成，多官能团耐受性，催化剂和试剂的低成本以及容易获得的起始原料的特征。使用这种方法，已经合成了生物学上相关的各种芳基取代的等渗酸。还已经用1,2-二氯乙烷评估了2-乙酰氨基-3-芳基丙烯酸酯的环化，这导致了5-甲基取代的等渗酸的重排环化产物。
• Supramolecular chiral phosphorous ligands based on a [2]pseudorotaxane complex for asymmetric hydrogenation
  作者：Yong Li、Yu Feng、Yan-Mei He、Fei Chen、Jie Pan、Qing-Hua Fan

  DOI：10.1016/j.tetlet.2008.03.039

  日期：2008.4

  A new type of supramolecular chiral phosphorus-based ligands was prepared from easily available monodentate ligands through complexation between dibenzylammonium salt and dibenzo[24]crown-8 macrocycle. Rhodium complexes with these supramolecular ligands were prepared, and the supramolecular bidentate ligand-containing catalyst has demonstrated better catalytic activity for all substrates, and higher

  一种新型的超分子手性磷基配体是通过二苄基铵盐与二苯并[24] crown-8大环之间的络合，由易于获得的单齿配体制备的。制备了具有这些超分子配体的铑配合物，含α-超分子双齿配体的催化剂对所有底物均表现出更好的催化活性，除了邻位取代的底物比在α不对称氢化中从母体单齿配体获得的底物更高的对映选择性-脱氢氨基酸酯。
• Rhodium‐Catalyzed ON‐OFF Switchable Hydrogenation Using a Molecular Shuttle Based on a [2]Rotaxane with a Phosphine Ligand
  作者：Yu‐Ping Tang、Yi‐Er Luo、Jun‐Feng Xiang、Yan‐Mei He、Qing‐Hua Fan

  DOI：10.1002/anie.202200638

  日期：2022.4.4

  A molecular shuttle based on a [2]rotaxane with a phosphine ligand has been applied to the rhodium-catalyzed hydrogenation of α,β-dehydroamino acid esters and aryl enamides. The hydrogenation can be switched ON/OFF efficiently by adjusting the movement of the rotaxane wheels with acid/base. Mechanistic studies have revealed that the formation of inactive RhIII-hydride species might be the reason for

  基于具有膦配体的 [2] 轮烷的分子穿梭已应用于铑催化的 α,β-脱氢氨基酸酯和芳基烯酰胺的氢化。通过用酸/碱调节轮烷轮的运动，可以有效地打开/关闭氢化。机理研究表明，非活性 Rh III氢化物的形成可能是反应停止的原因。
• Axial 4,4′,6,6′-Tetrakis-trifluoromethyl-biphenyl-2,2′-diamine (TF-BIPHAM): Resolution and Applications in Asymmetric Hydrogenation
  作者：Chun-Jiang Wang、Feng Gao、Gang Liang

  DOI：10.1021/ol8018677

  日期：2008.11.6

  The racemic TF-BIPHAM was resolved for the first time, and the effectiveness of the resolved diamine was demonstrated by highly enantioselective hydrogenation of alpha-aryl enamides and (x-dehydroamino acid esters using readily accessible bis(aminophosphine) ligands.
• Dendritic MonoPhos: synthesis and application in Rh-catalyzed asymmetric hydrogenation
  作者：Wei-Jun Tang、Yi-Yong Huang、Yan-Mei He、Qing-Hua Fan

  DOI：10.1016/j.tetasy.2006.01.013

  日期：2006.2

  A new class of dendritic monodentate phosphoramidite ligands were synthesized through substitution of the dimethylamino moiety in MonoPhos by the Frechet-type dendritic wedge and applied in the asymmetric hydrogenation of alpha-dehydroamino acid esters and dimethyl itaconate. High enantioselectivities (up to 97.9% ee) and catalytic activities (up to 4850 h(-1) TOF) were achieved, which are better or comparable to those obtained from MonoPhos. The third generation dendrimer catalyst gave the slightly lower catalytic activity relative to the lower generation ones. The steric shielding by the dendrimer could stabilize the rhodium complex against decomposition caused by hydrolysis in a protic solvent. The inactive catalysts (RhL3 and RhL4) were activated by addition of a free metal precursor Rh(COD)(2)BF4, and showed high enantioselectivities and catalytic activities. (c) 2006 Elsevier Ltd. All rights reserved.