(E)-3-cyclohexyl-N-methylacrylamide | 848477-86-1

• 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: (E)-3-cyclohexyl-N-methylacrylamide
• 英文别名: (E)-3-cyclohexyl-N-methylprop-2-enamide
• CAS: 848477-86-1
• 化学式: C₁₀H₁₇NO
• 分子量: 167.251
• InChiKey: ZOCNWUOYKKXXQM-BQYQJAHWSA-N

物化性质

• 熔点：
  82-83 °C
• 沸点：
  322.3±15.0 °C(Predicted)
• 密度：
  1.014±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 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：

  (E)-3-cyclohexyl-N-methylacrylamide 在 叔丁基过氧化氢 三苯胂氧化物 、 S-1,1'-联-2-萘酚 、 samarium(III) isopropoxide 作用下， 以 四氢呋喃 、 癸烷 为溶剂， 反应 91.0h， 生成
  参考文献：
  名称：

  Dynamic Ligand Exchange of the Lanthanide Complex Leading to Structural and Functional Transformation:  One-Pot Sequential Catalytic Asymmetric Epoxidation-Regioselective Epoxide-Opening Process

  摘要：

  The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various a,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samariurn azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.

  DOI：

  10.1021/ja043770+
• 作为产物：
  描述：

  3-cyclohexyl-N-methylpropiolamide 在 potassium tert-butylate 、 频那醇硼烷 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以62%的产率得到
  参考文献：
  名称：

  丙炔酰胺衍生物的催化、无过渡金属半还原：范围和机理研究。

  摘要：

  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。

  DOI：

  10.1021/acs.orglett.0c02567

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。
• 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。
• 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。
• Dynamic Ligand Exchange of the Lanthanide Complex Leading to Structural and Functional Transformation:  One-Pot Sequential Catalytic Asymmetric Epoxidation-Regioselective Epoxide-Opening Process
  作者：Shin-ya Tosaki、Riichiro Tsuji、Takashi Ohshima、Masakatsu Shibasaki

  DOI：10.1021/ja043770+

  日期：2005.2.1

  The characteristic property of the lanthanide complex, which easily undergoes a dynamic ligand exchange and alters its structure and function in situ, is described. After the completion of the catalytic asymmetric epoxidation of various a,beta-unsaturated amides 2 in the presence of the Sm-(S)-BINOL-Ph3As=O (1:1:1) complex 1 (2-10 mol %), the addition of Me3SiN3 directly to the reaction mixture led to smooth epoxide-opening at room temperature, affording the corresponding anti-beta-azido-alpha-hydroxyamide 4 in excellent overall yield (up to 99%) with complete regioselectivity and excellent enantiomeric excess (up to >99%). The key to the success of the sequential process was the in situ generation of the highly reactive samarium azide complex through dynamic ligand exchange. In situ IR spectroscopy and other experiments provided strong evidence that the samariurn azide complex was generated. In addition, the relatively high Lewis basicity of the amide moiety had a key role in the high reactivity of both the epoxidation and the epoxide-opening reactions. Examinations of other nucleophiles such as sulfur or carbon nucleophiles as well as transformations of epoxide-opened products are also described.