(E)-N,N-diethyl-2,5-dimethylhex-2-enamide | 948916-66-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-N,N-diethyl-2,5-dimethylhex-2-enamide
• CAS: 948916-66-3
• 化学式: C₁₂H₂₃NO
• 分子量: 197.321
• InChiKey: QXRCISOXPVBGAF-PKNBQFBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  四氯化碳 、 (E)-N,N-diethyl-2,5-dimethylhex-2-enamide 在 chromium dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以66%的产率得到(1S*,2S*,3R*)-2-chloro-N,N-diethyl-3-isobutyl-1-methylcyclopropanecarboxamide
  参考文献：
  名称：

  α，β-不饱和酰胺的高度立体选择性卤代丙烷

  摘要：

  从二-三-或四取代的（氯-和bromocyclopropanamides的一种方便的高度立体选择性合成ë） -或（Ž）-α，β -与由二氯化铬或二溴化物促进总或高立体选择性不饱和酰胺进行说明。还报道了氯环丙烷酰胺向相应的酮或胺的转化。提出了一种解释这些转换的机制。

  DOI：

  10.1002/adsc.200900331
• 作为产物：
  描述：

  2,2-二氯-N,N-二乙基乙酰胺 在 2-苯基吡啶 、 manganese chloride bis(lithium chloride) 、 lithium 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.25h， 生成 (E)-N,N-diethyl-2,5-dimethylhex-2-enamide
  参考文献：
  名称：

  Sequential Reactions Promoted by Manganese:  Completely Stereoselective Synthesis of (E)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids

  摘要：

  A complete E-selective synthesis of a,alpha,beta-unsaturated amides through a sequential reaction of a range of dichloroamides with a variety of aldehydes promoted by Rieke manganese (Mn*) is reported. A mechanism based on a sequential aldol-type reaction and a completely stereoselective beta-elimination is proposed to explain these results. The unsaturated amides obtained are readily and efficiently transformed into alpha,beta-unsaturated ketones, aldehydes, or carboxylic acids without loss of the diastereoisomeric purity of the C-C double bond.

  DOI：

  10.1021/jo701417z

文献信息

• Stereoselective Olefination Reactions Promoted by Rieke Manganese
  作者：José Concellón、Humberto Rodríguez-Solla、Vicente del Amo、Pamela Díaz

  DOI：10.1055/s-0029-1216880

  日期：2009.8

  applied to develop a novel and direct synthesis of (E)-α,β-unsaturated esters or amides and (Z)-α,β-unsaturated α-halo esters and α-choroamides through a Mn*-mediated sequential olefination protocol of aldehydes with dichloro esters or amides and trihalo esters or trichloroamides, respectively. manganese - elimination reactions - stereoselectivity - α,β-unsaturated esters - α,β-unsaturated amides - metalation

  提出了使用廉价的无毒金属锰进行立体选择性β-消除反应并促进醛的顺序烯化反应以获得α，β-不饱和酯和酰胺的优势的研究。使用活性锰（Mn *）作为金属化剂进行了各种消除反应，所有这些反应均具有完全的立体选择性和高收率的特征。锰的这种能力已被用于开发通过Mn *-直接合成（E）-α，β-不饱和酯或酰胺与（Z）-α，β-不饱和α-卤代酯和α-氯酰胺的新颖而直接的合成方法。介导的醛分别与二氯酯或酰胺和三卤代酯或三氯酰胺的顺序烯烃化方案。 锰-消除反应-立体选择性-α，β-不饱和酯-α，β-不饱和酰胺-金属化
• CrCl₂-Promoted Stereospecific and Stereoselective Alkyl- and Silylcyclopropanation of α,β-Unsaturated Amides
  作者：José M. Concellón、Humberto Rodríguez-Solla、Carmen Méjica、Elena G. Blanco、Santiago García-Granda、M. Rosario Díaz

  DOI：10.1021/jo800103t

  日期：2008.5.1

  An efficient chromium-promoted alkyl- or silylcyclopropanation of α,β-unsaturated amides is described. These reactions can be carried out on (E)- or (Z)-α,β-enamides in which the C−C double bond is di-, or trisubstituted. This process takes place with total stereospecificity and the new stereogenic center is generated with high or total stereoselectivity. Some synthetic applications of the obtained

  描述了一种有效的铬促进的α，β-不饱和酰胺的烷基或甲硅烷基环丙烷化。这些反应可以在（C）C双键被二或三取代的（E）-或（Z）-α，β-酰胺上进行。该过程以完全立体特异性进行，并且以高或总体立体选择性产生了新的立体异构中心。还报道了所得甲硅烷基环丙基酰胺的一些合成应用。已经提出了基于类胡萝卜素或卡宾配合物的生成的两种机理来解释该环丙烷化反应。
• Sequential Reactions Promoted by Manganese:  Completely Stereoselective Synthesis of (<i>E</i>)-α,β-Unsaturated Amides, Ketones, Aldehydes, and Carboxylic Acids
  作者：José M. Concellón、Humberto Rodríguez-Solla、Pamela Díaz

  DOI：10.1021/jo701417z

  日期：2007.10.1

  A complete E-selective synthesis of a,alpha,beta-unsaturated amides through a sequential reaction of a range of dichloroamides with a variety of aldehydes promoted by Rieke manganese (Mn*) is reported. A mechanism based on a sequential aldol-type reaction and a completely stereoselective beta-elimination is proposed to explain these results. The unsaturated amides obtained are readily and efficiently transformed into alpha,beta-unsaturated ketones, aldehydes, or carboxylic acids without loss of the diastereoisomeric purity of the C-C double bond.
• Highly Stereoselective Halocyclopropanation of α,β-Unsaturated Amides
  作者：José M. Concellón、Humberto Rodríguez-Solla、Elena G. Blanco、María A. Villa-García、Noemí Alvaredo、Santiago García-Granda、M. Rosario Díaz

  DOI：10.1002/adsc.200900331

  日期：2009.9

  A convenient highly stereoselective synthesis of chloro- and bromocyclopropanamides from di- tri- or tetrasubstituted (E)- or (Z)-α,β-unsaturated amides with total or high stereoselectivity promoted by chromium dichloride or dibromide is described. The transformation of chlorocyclopropanamides into the corresponding ketones or amines is also reported. A mechanism to explain these transformations is

  从二-三-或四取代的（氯-和bromocyclopropanamides的一种方便的高度立体选择性合成ë） -或（Ž）-α，β -与由二氯化铬或二溴化物促进总或高立体选择性不饱和酰胺进行说明。还报道了氯环丙烷酰胺向相应的酮或胺的转化。提出了一种解释这些转换的机制。