(Z)-N-methyl-3-phenylacrylamide | 64330-04-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (Z)-N-methyl-3-phenylacrylamide
• 英文别名: (Z)-N-methyl-3-phenylprop-2-enamide
• CAS: 64330-04-7
• 化学式: C₁₀H₁₁NO
• 分子量: 161.203
• InChiKey: JNXLTSSPACJLEG-FPLPWBNLSA-N

物化性质

• 沸点：
  354.3±25.0 °C(Predicted)
• 密度：
  1.054±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-N-methyl-3-phenylacrylamide 以 二氯甲烷 为溶剂， 生成 (E)-N-methyl-3-phenyl-acrylamide
  参考文献：
  名称：

  Lewis-acid catalysis of photochemical reactions. 9. Structure and photoisomerization of (E)- and (Z)-cinnamamides and their Lewis acid complexes

  摘要：

  The spectroscopic properties and photoisomerization reactions of several (E)- and (Z)-cinnamamides have been investigated in the absence and presence of the strong Lewis acid BF3. The (E)-cinnamamides are essentially planar and exist predominantly in the enone s-cis conformation, except in the case of the alpha-methyl tertiary amide which adopts the s-trans conformation in order to minimize nonbonded repulsion. The (Z)-cinnamamides exist predominantly in the highly nonplanar s-trans conformation. This unusual conformational preference is attributed to intramolecular charge transfer from the aromatic to amide functionality. Photoisomerization efficiencies are dependent upon N-alkylation, aromatic substitution, alpha-alkylation, solvent, and excitation wavelength. These effects are attributed to the existence of two lowest energy pi,pi* singlet states (one reactive and one nonreactive) whose relative energies are dependent upon substitution. The cinnamamides from 1:1 complexes with BF3 with equilibrium constants > 10(3). Complexation alters both the electronic structure and photochemical behavior of the cinnamamides. Quantitative E --> Z isomerization has been observed for the BF3 complexes of two tertiary amides.

  DOI：

  10.1021/jo00002a015
• 作为产物：
  描述：

  (E)-N-methyl-3-phenyl-acrylamide 以 二氯甲烷 为溶剂， 生成 (Z)-N-methyl-3-phenylacrylamide
  参考文献：
  名称：

  (E)-肉桂酰胺的构型依赖光异构化

  摘要：

  Effets des substituants de l'azote et du cycle benzenique sur la photoisomerisation dans l'UV proche des composes ci-dessus

  DOI：

  10.1021/ja00223a048

文献信息

• Catalytic, Transition-Metal-Free Semireduction of Propiolamide Derivatives: Scope and Mechanistic Investigation
  作者：R. Justin Grams、Christopher J. Garcia、Connor Szwetkowski、Webster L. Santos

  DOI：10.1021/acs.orglett.0c02567

  日期：2020.9.4

  We report a transition-metal-free trans-selective semireduction of alkynes with pinacolborane and catalytic potassium tert-butoxide. A variety of 3-substituted primary and secondary propiolamides, including an analog of FK866, a potent nicotinamide mononucleotide adenyltransferase (NMNAT) inhibitor, are reduced to the corresponding (E)-3-substituted acrylamide derivatives in up to 99% yield with >99:1

  我们报道了频哪醇硼烷和催化叔丁醇钾对炔烃的无过渡金属反式选择性半还原。各种 3-取代的一级和二级丙炔酰胺，包括 FK866 的类似物（一种有效的烟酰胺单核苷酸腺苷酸转移酶 (NMNAT) 抑制剂），可被还原为相应的 ( E )-3-取代的丙烯酰胺衍生物，产率高达 99%，且 >99 ：1 E / Z选择性。机理研究表明，活化的路易斯酸碱配合物将氢化物转移到α-碳上，然后以反式方式快速质子化。
• Organocatalytic <i>Trans</i> Semireduction of Primary and Secondary Propiolamides: Substrate Scope and Mechanistic Studies
  作者：R. Justin Grams、Monsurat M. Lawal、Connor Szwetkowski、Daniel Foster、Carol Ann Rosenblum、Carla Slebodnick、Valerie Vaissier Welborn、Webster L. Santos

  DOI：10.1002/adsc.202101020

  日期：2022.1.4

  We report a chemoselective, phosphine-catalyzed semireduction of primary and secondary propiolamides. In the presence of stoichiometric pinacolborane and catalytic n-tributylphosphine, a variety of propiolamides were successfully converted to the corresponding acrylamides in excellent yield with (E)-stereoselectivity. The reaction condition is tolerant of various functional groups including alkene

  我们报告了初级和次级丙酰胺的化学选择性、膦催化的半还原反应。在化学计量的频哪醇硼烷和催化正三丁基膦的存在下，各种丙酰胺以优异的收率成功转化为相应的丙烯酰胺，具有（E）-立体选择性。反应条件可以容忍各种官能团，包括烯烃、炔烃、酮或酯。氘标记研究表明，来自活化频哪醇硼烷的氢化物被添加到 α-碳，酰胺氮上的质子被 β-碳提取以提供 ( E )-丙烯酰胺。DFT 计算揭示了 ( E )- 在 ( Z)-异构体。
• Mild Zinc-Promoted Horner-Wadsworth-Emmons Reactions of Diprotic Phosphonate Reagents
  作者：Paul Helquist、Douglas Schauer

  DOI：10.1055/s-2006-950292

  日期：2006.11

  We report the development of a mild protocol for the Horner-Wadsworth-Emmons reaction of diprotic phosphonates that makes use of a zinc triflate promoter in the presence of mild tertiary amine bases to produce α,β-unsaturated carboxylic acids and amides.

  我们报道了一种温和的二羧酸膦酸酯进行Horner-Wadsworth-Emmons反应的方法，该方法在温和的三级胺碱存在下利用三氟甲磺酸锌作为催化剂，生成α,β-不饱和羧酸和酰胺。
• Manganese Catalyzed Enantioselective Epoxidation of <i>α</i> , <i>β</i> ‐Unsaturated Amides with H ₂ O ₂
  作者：Roman V. Ottenbacher、Vladimir I. Kurganskiy、Evgenii P. Talsi、Konstantin P. Bryliakov

  DOI：10.1002/adsc.202100198

  日期：2021.6.8

  Herewith, we report the enantioselective epoxidation of electron-deficient cis- and trans-α,β-unsaturated amides with the environmentally benign oxidant H2O2. The catalysts - manganese complexes with bis-amino-bis-pyridine and structurally related ligands - exhibit reasonably high efficiency (up to 100 TON) and excellent chemo- and enantioselectivity (up to 100% and 99% ee, respectively). Crucially

  在此，我们报告了缺电子顺式和反式-α，β-不饱和酰胺与环境友好型氧化剂H 2 O 2的对映选择性环氧化反应。催化剂——锰与双氨基双吡啶和结构相关配体的配合物——表现出相当高的效率（高达 100 吨）和优异的化学和对映选择性（分别高达 100% 和 99% ee）。至关重要的是，顺式-enamides环氧化的对映选择性和产率用NH部分的存在，其效果可以通过之间的氢键相互作用来解释被显着增强的顺-烯酰胺底物和锰基氧转移物质。
• Configuration-dependent photoisomerization of (E)-cinnamamides
  作者：Frederick D. Lewis、Jeffrey E. Elbert、Alana L. Upthagrove、Paul D. Hale

  DOI：10.1021/ja00223a048

  日期：1988.7

  Effets des substituants de l'azote et du cycle benzenique sur la photoisomerisation dans l'UV proche des composes ci-dessus

  Effets des substituants de l'azote et du cycle benzenique sur la photoisomerisation dans l'UV proche des composes ci-dessus