(E)-N,N-Diisopropyl-2-methyl-3-phenylpropenamide

• 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: (E)-N,N-Diisopropyl-2-methyl-3-phenylpropenamide
• 英文别名: (E)-N,N-diisopropyl-2-methyl-3-phenylacrylamide；(E)-2-methyl-3-phenyl-N,N-di(propan-2-yl)prop-2-enamide
• 化学式: C₁₆H₂₃NO
• 分子量: 245.365
• InChiKey: WJAGIRFDOAXSBG-SDNWHVSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 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：

  (E)-N,N-Diisopropyl-2-methyl-3-phenylpropenamide 在 钯 氢气 作用下， 生成 N,N-diisopropyl-2-methyl-3-phenylpropanamide
  参考文献：
  名称：

  Complex induced proximity effects: .beta.-lithiations of carboxamides

  摘要：

  The R*,S* and the R*,R* diastereomers of N,N-diisopropyl-2,3-dideuterio-2-methyl-3-phenylpropanamide (5,6) have been used to investigate the diastereoselectivity of the beta-lithiation of N,N-diisopropyl-2-methyl-3-phenylpropanamide (4). The beta-lithiation of 4 is highly diastereoselective with the beta-proton that is in the same relative position as the beta-proton of diastereomer 6 being preferentially removed. The beta-lithio species derived from 4 is shown to be a pyramidal, organolithium reagent based on C-13 NMR. Lithiation of the R*,S* and the R*,R* diastereomers of N,N-diisopropyl-2-methyl-3-(phenylthio)butanamide (7, 8) and N,N-diisopropyl-2,3-dimethyl-4-pentenamide (9, 10) occur at the beta-position. Lithiation of the R*,S* and R*,R* diastereomers of N,N-diisopropyl-2-methyl-3-phenylbutanamide (11, 12) occurs at the beta-position for 11 and at the alpha-position for 12. A conformational model is shown to correlate with these observations. The beta-lithio species formed do not react diastereospecifically.

  DOI：

  10.1021/jo00016a025
• 作为产物：
  描述：

  2-chloropropionic acid diisopropylamide acid 在 samarium diiodide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 13.17h， 生成 (E)-N,N-Diisopropyl-2-methyl-3-phenylpropenamide
  参考文献：
  名称：

  Synthesis of (E)-α,β-Unsaturated Amides with High Selectivity by Using Samarium Diiodide

  摘要：

  Stereoselective beta -elimination of 2-chloro-3-hydroxyamides 1 is achieved by using samarium diiodide to yield alpha,beta -unsaturated amides 2, in which the C=C bond is di- tri-, or tetrasubstituted. The starting compounds a are easily prepared by reaction of the corresponding lithium enolates of alpha -chloroamides with aldehydes or ketones at -78 degreesC. The influence of the reaction conditions and the structure of the starting compounds on the stereoselectivity of the beta -elimination reaction is also discussed.

  DOI：

  10.1002/1521-3765(20010716)7:14<3062::aid-chem3062>3.0.co;2-f

文献信息

• Undirected Arene and Chelate-Assisted Olefin C-H Bond Activation: [Rh^IIICp*]-Catalyzed Dehydrogenative Alkene-Arene Coupling as a New Pathway for the Selective Synthesis of Highly Substituted<i>Z</i>Olefins
  作者：Joanna Wencel-Delord、Corinna Nimphius、Frederic W. Patureau、Frank Glorius

  DOI：10.1002/asia.201101018

  日期：2012.6

  Undirected/Directed Cross‐Coupling: A new dehydrogenative RhIII‐catalyzed cross‐coupling reaction between bromoarenes bearing no directing group and vinylic substrates substituted by a chelating group is reported. An original reaction mechanism enables the use of internal alkenes in a Z‐selective coupling. The application of 1,3‐disubstituted or 1,2‐homodisubstituted arenes leads to the formation of highly functionalized

  无定向/定向交叉偶联：报道了不带导向基团的溴代芳烃与被螯合基团取代的乙烯基底物之间发生的新的脱氢Rh III催化的交叉偶联反应。原始的反应机理可以在Z选择性偶合中使用内部烯烃。1,3-二取代或1,2-同二取代的芳烃的应用导致形成高度官能化，复杂且有价值的烯烃作为一种单一异构体。
• Stereospecific Cyclopropanation of Highly Substituted C−C Double Bonds Promoted by CrCl₂. Stereoselective Synthesis of Cyclopropanecarboxamides and Cyclopropyl Ketones
  作者：José M. Concellón、Humberto Rodríguez-Solla、Carmen Méjica、Elena G. Blanco

  DOI：10.1021/ol070896d

  日期：2007.8.1

  (Z)-alpha,beta-enamides in which the C-C double bond is di-, tri-, or tetrasubstituted. In all cases the process is completely stereospecific and only a single diastereoisomer is obtained. In addition, cyclopropyl ketones were readily prepared by reaction of the cyclopropanecarboxamides (derived from morpholine) obtained with a range of organolithium compounds. A mechanism has been proposed to explain the cyclopropanation

  我们在这里描述了CrCl（2）促进的α，β-不饱和酰胺的环丙烷化。该反应可以在其中CC双键被二，三或四取代的（E）-或（Z）-α，β-烯酰胺上进行。在所有情况下，该过程都是完全立体定向的，并且仅获得单个非对映异构体。另外，通过使所获得的环丙烷甲酰胺（衍生自吗啉）与一定范围的有机锂化合物反应，可以容易地制备环丙基酮。已经提出了解释环丙烷化反应的机理。
• 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。
• Photoisomerization of Alkenes via Energy Transfer Enabled by Cu‐Acetylide Complexes
  作者：Ryo Murakami、Noritaka Kojima、Ryoya Kamo、Hiroto Tanishima、Fuyuhiko Inagaki

  DOI：10.1002/ejoc.202300948

  日期：2023.12.19

  visible photosensitizers for energy transfer to alkenes. On this basis, the E→Z photoisomerization reactions of alkenes with various functional groups under blue light irradiation were performed with moderate to high selectivity. The mechanistic studies suggested that the reactions involved energy transfer (EnT) from the photo-excited copper acetylide to the alkene via the singlet excited state.

  人们发现乙炔铜配合物可作为可见光敏剂，将能量转移至烯烃。在此基础上，在蓝光照射下进行了具有不同官能团的烯烃的E→Z光异构化反应，具有中等到高选择性。机理研究表明，该反应涉及从光激发乙炔铜通过单重激发态到烯烃的能量转移（EnT）。
• Synthesis of (E)-α,β-Unsaturated Amides with High Selectivity by Using Samarium Diiodide
  作者：José M. Concellón、Juan A. Pérez-Andrés、Humberto Rodríguez-Solla

  DOI：10.1002/1521-3765(20010716)7:14<3062::aid-chem3062>3.0.co;2-f

  日期：2001.7.16

  Stereoselective beta -elimination of 2-chloro-3-hydroxyamides 1 is achieved by using samarium diiodide to yield alpha,beta -unsaturated amides 2, in which the C=C bond is di- tri-, or tetrasubstituted. The starting compounds a are easily prepared by reaction of the corresponding lithium enolates of alpha -chloroamides with aldehydes or ketones at -78 degreesC. The influence of the reaction conditions and the structure of the starting compounds on the stereoselectivity of the beta -elimination reaction is also discussed.