1,3-dimethyl-3-phenyl-1-(1-phenylvinyl)urea | 1227083-34-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,3-dimethyl-3-phenyl-1-(1-phenylvinyl)urea
• 英文别名: 1,3-dimethyl-1-phenyl-3-(1-phenylvinyl)urea；1,3-Dimethyl-1-phenyl-3-(1-phenylethenyl)urea；1,3-dimethyl-1-phenyl-3-(1-phenylethenyl)urea
• CAS: 1227083-34-2
• 化学式: C₁₇H₁₈N₂O
• 分子量: 266.343
• InChiKey: WMOGPVCHMOSEHW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1,3-dimethyl-3-phenyl-1-(1-phenylvinyl)urea 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 以30%的产率得到1-(2,2-dibromo-1-phenyl-vinyl)-1,3-dimethyl-3-phenyl-urea
  参考文献：
  名称：

  Geometry-Selective Synthesis of E or Z N-Vinyl Ureas (N-Carbamoyl Enamines)

  摘要：

  N-Vinyl ureas are emerging as a valuable class of compounds with both nucleophilic and electrophilic reactivity. They may be made by capturing the enamine tautomer of an imine with an isocyanate, a reaction which in general leads to the E isomer of the vinyl urea. Deprotonation of such a vinyl urea, or of an allyl urea, generates a dipole stabilized Z-allyl anion which may be protonated to return the Z-vinyl urea. Isomerization of an allyl urea with a Ru complex provides an alternative route to E-vinyl ureas.

  DOI：

  10.1021/ol1027442
• 作为产物：
  描述：

  (1Z)-N-甲基-1-苯基乙烷亚胺 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 1,3-dimethyl-3-phenyl-1-(1-phenylvinyl)urea
  参考文献：
  名称：

  Geometry-Selective Synthesis of E or Z N-Vinyl Ureas (N-Carbamoyl Enamines)

  摘要：

  N-Vinyl ureas are emerging as a valuable class of compounds with both nucleophilic and electrophilic reactivity. They may be made by capturing the enamine tautomer of an imine with an isocyanate, a reaction which in general leads to the E isomer of the vinyl urea. Deprotonation of such a vinyl urea, or of an allyl urea, generates a dipole stabilized Z-allyl anion which may be protonated to return the Z-vinyl urea. Isomerization of an allyl urea with a Ru complex provides an alternative route to E-vinyl ureas.

  DOI：

  10.1021/ol1027442

文献信息

• Tandem β-Alkylation−α-Arylation of Amines by Carbolithiation and Rearrangement of <i>N</i>-Carbamoyl Enamines (Vinyl Ureas)
  作者：Jonathan Clayden、Morgan Donnard、Julien Lefranc、Alberto Minassi、Daniel J. Tetlow

  DOI：10.1021/ja1007992

  日期：2010.5.19

  an umpolung fashion to the beta-carbon of N-carbamoyl enamines (N-vinyl ureas). The reaction proceeds with syn diastereospecificity and provides urea-stabilized, configurationally defined organolithiums. Facilitated by coordinating solvents (THF or DMPU), these undergo intramolecular attack on an N'-aryl group, resulting in retentive arylation of the organolithium and hence overall addition of an alkyl

  有机锂以 umpolung 方式添加到 N-氨基甲酰基烯胺（N-乙烯基脲）的 β-碳上。该反应以顺式非对映特异性进行，并提供尿素稳定的、构型确定的有机锂。在配位溶剂（THF 或 DMPU）的促进下，它们对 N'-芳基进行分子内攻击，导致有机锂的保留性芳基化，从而将烷基或芳基整体添加到脲取代烯烃的两个碳原子上。在热丁醇中轻松脱保护允许快速、多组分构建重取代胺。
• Photocatalytic Difunctionalization of Vinyl Ureas by Radical Addition Polar Truce–Smiles Rearrangement Cascades
  作者：Roman Abrams、Jonathan Clayden

  DOI：10.1002/anie.202003632

  日期：2020.7.6

  We report tandem alkyl‐arylations and phosphonyl‐arylations of vinyl ureas by way of a photocatalytic radical‐polar crossover mechanism. Addition of photoredox‐generated radicals to the alkene forms a new C−C or C−P bond and generates a product radical adjacent to the urea function. Reductive termination of the photocatalytic cycle generates an anion that undergoes a polar Truce–Smiles rearrangement

  我们通过光催化自由基-极性交叉机理报告了乙烯基脲的串联烷基芳基化和膦酰基芳基化。光氧化还原产生的自由基加到烯烃上会形成一个新的C C或C P键，并产生一个与脲官能团相邻的产物自由基。光催化循环的还原性终止产生一个阴离子，该阴离子经历一个极性的Truce-Smiles重排，形成一个CC键。该反应以一系列的α-氟化烷基亚磺酸钠盐和二芳基膦氧化物为自由基前体而成功，并且构象加速的Truce-Smiles重排不受迁移的芳香环电子性质的限制。形式上，该反应构成了碳-碳双键的α，β-泛函化，并在可见光和易于获得的有机光催化剂的温和条件下进行。产物是通常用F或P取代基官能化的α，α-二芳基烷基脲，可以很容易地转化为α，α-二芳基烷基胺。
• Carbolithiation of <i>N</i>-alkenyl ureas and <i>N</i>-alkenyl carbamates
  作者：Julien Lefranc、Alberto Minassi、Jonathan Clayden

  DOI：10.3762/bjoc.9.70

  日期：——

  N-Alkenyl ureas and N-alkenyl carbamates, like other N-acyl enamines, are typically nucleophilic at their β-carbon. However, by incorporating an α-aryl substituent, we show that they will also undergo attack at the β-carbon by organolithium nucleophiles, leading to the products of carbolithiation. The carbolithiation of E and Z N-alkenyl ureas is diastereospecific, and N-tert-butoxycarbonyl N-alkenyl carbamates give carbolithiation products that may be deprotected in situ to provide a new connective route to hindered amines.

  N-烯基脲和N-烯基氨基甲酸酯，像其他N-酰基烯胺一样，通常在其β-碳上具有亲核性。然而，通过引入α-芳基取代基，我们表明它们也会被有机锂亲核试剂攻击β-碳，从而导致碳锂化产物。N-烯基脲的碳锂化是立体选择性的，N-叔丁氧羰基N-烯基氨基甲酸酯产生的碳锂化产物可以原位去保护，提供一种新的连接通路到阻隔胺。
• Geometry-Selective Synthesis of <i>E</i> or <i>Z</i> <i>N</i>-Vinyl Ureas (<i>N</i>-Carbamoyl Enamines)
  作者：Julien Lefranc、Daniel J. Tetlow、Morgan Donnard、Alberto Minassi、Erik Gálvez、Jonathan Clayden

  DOI：10.1021/ol1027442

  日期：2011.1.21

  N-Vinyl ureas are emerging as a valuable class of compounds with both nucleophilic and electrophilic reactivity. They may be made by capturing the enamine tautomer of an imine with an isocyanate, a reaction which in general leads to the E isomer of the vinyl urea. Deprotonation of such a vinyl urea, or of an allyl urea, generates a dipole stabilized Z-allyl anion which may be protonated to return the Z-vinyl urea. Isomerization of an allyl urea with a Ru complex provides an alternative route to E-vinyl ureas.