[Cl2NN]Cu-OtBu | 1215209-38-3

• 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: [Cl2NN]Cu-OtBu
• 英文别名: [Cl₂NN]Cu-OtBu；[Cu(CH(C(CH3)NC6H3Cl2)2)(O(tert-butyl))]
• CAS: 1215209-38-3
• 化学式: C₂₁H₂₂Cl₄CuN₂O
• 分子量: 523.776
• InChiKey: DWRVUSWQIPCHJR-SOQGGHQASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  2-氨基吡啶 、 [Cl2NN]Cu-OtBu 以 正戊烷 为溶剂， 反应 0.08h， 以25%的产率得到[Cl₂NN]Cu(κ²-2-aminopyridine(-H))
  参考文献：
  名称：

  Copper(II) Anilides in sp³ C-H Amination

  摘要：

  We report a series of novel beta-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H2NAr (Ar = 2,4,6-Cl3C6H2 (Ar-Cl3), 3,5-(CF3)(2)C6H3 (Ar-F6), or 2-py) with the copper(II) t-butoxide complex [Cl2NN]-Cu-(OBu)-O-t yields the corresponding copper(II) anilides [Cl2NN]-Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: kappa(1)-N in the trigonal [Cl2NN]Cu-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}(2)(mu-NHArF6)(2) and kappa(2)-N,N in the square planar [Cl2NN]Cu(kappa(2)-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a pi-stacking arrangement of [Cl2NN]Cu-NHArCl3; solution EPR data are consistent with monomeric species. Reaction of [Cl2NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when (BuOOBu)-Bu-t-Bu-t is used, which allows for HAA of R-H to occur from the (BuO center dot)-Bu-t radical generated by reaction of [Cl2NN]Cu and (BuOOBu)-Bu-t-Bu-t. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R-center dot generated from HAA by (BuO center dot)-Bu-t to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction.

  DOI：

  10.1021/ja5026547
• 作为产物：
  描述：

  [Cl₂NN]Cu(κ²-2-aminopyridine(-H)) 以 氘代苯 、 正戊烷 为溶剂， 反应 0.66h， 生成 [Cl2NN]Cu-OtBu
  参考文献：
  名称：

  Copper(II) Anilides in sp³ C-H Amination

  摘要：

  We report a series of novel beta-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H2NAr (Ar = 2,4,6-Cl3C6H2 (Ar-Cl3), 3,5-(CF3)(2)C6H3 (Ar-F6), or 2-py) with the copper(II) t-butoxide complex [Cl2NN]-Cu-(OBu)-O-t yields the corresponding copper(II) anilides [Cl2NN]-Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: kappa(1)-N in the trigonal [Cl2NN]Cu-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}(2)(mu-NHArF6)(2) and kappa(2)-N,N in the square planar [Cl2NN]Cu(kappa(2)-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a pi-stacking arrangement of [Cl2NN]Cu-NHArCl3; solution EPR data are consistent with monomeric species. Reaction of [Cl2NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when (BuOOBu)-Bu-t-Bu-t is used, which allows for HAA of R-H to occur from the (BuO center dot)-Bu-t radical generated by reaction of [Cl2NN]Cu and (BuOOBu)-Bu-t-Bu-t. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R-center dot generated from HAA by (BuO center dot)-Bu-t to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction.

  DOI：

  10.1021/ja5026547
• 作为试剂：
  描述：

  2,4,6-三氯苯胺 在 二叔丁基过氧化物 、 [Cl2NN]Cu-OtBu 作用下， 以 正戊烷 为溶剂， 反应 24.08h， 生成 N-(+/-)-α-methylbenzyl-N-2,4,6-trichlorobenzylamine
  参考文献：
  名称：

  Copper(II) Anilides in sp³ C-H Amination

  摘要：

  We report a series of novel beta-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H2NAr (Ar = 2,4,6-Cl3C6H2 (Ar-Cl3), 3,5-(CF3)(2)C6H3 (Ar-F6), or 2-py) with the copper(II) t-butoxide complex [Cl2NN]-Cu-(OBu)-O-t yields the corresponding copper(II) anilides [Cl2NN]-Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: kappa(1)-N in the trigonal [Cl2NN]Cu-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}(2)(mu-NHArF6)(2) and kappa(2)-N,N in the square planar [Cl2NN]Cu(kappa(2)-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a pi-stacking arrangement of [Cl2NN]Cu-NHArCl3; solution EPR data are consistent with monomeric species. Reaction of [Cl2NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when (BuOOBu)-Bu-t-Bu-t is used, which allows for HAA of R-H to occur from the (BuO center dot)-Bu-t radical generated by reaction of [Cl2NN]Cu and (BuOOBu)-Bu-t-Bu-t. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R-center dot generated from HAA by (BuO center dot)-Bu-t to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction.

  DOI：

  10.1021/ja5026547

文献信息

• Catalytic CH Amination with Unactivated Amines through Copper(II) Amides
  作者：Stefan Wiese、Yosra M. Badiei、Raymond T. Gephart、Susanne Mossin、Matthew S. Varonka、Marie M. Melzer、Karsten Meyer、Thomas R. Cundari、Timothy H. Warren

  DOI：10.1002/anie.201003676

  日期：2010.11.15

  En route to catalysis: Two equivalents of the three‐coordinate copper(II) amide [(Cl2NN)Cu]‐NHAd participate in stoichiometric CH amination by a H‐atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert‐butoxide intermediate to allow for the unprecedented catalytic amination of sp3‐CH bonds with unactivated alkylamines. This method greatly expands

  途中催化：两个当量的三维坐标铜（II）酰胺[（CL的2 NN）的Cu] -NHAd参与化学计量Ç  ħ由H-原子夺取胺化/自由基捕获序列。这个活性种可以通过铜来产生（II）叔丁醇中间体以允许SP的前所未有的催化胺化3 -C 与未活化的烷基胺H键。该方法大大扩展了用于催化CH胺化反应的胺的范围，因为大多数方案都需要基于N的吸电子基团。
• [EN] CATALYTIC C-H BOND ACTIVATION<br/>[FR] ACTIVATION CATALYTIQUE DE LIAISONS C-H POUR LA SYNTHÈSE D'ÉTHERS ET DE THIOÉTHERS
  申请人：UNIV GEORGETOWN

  公开号：WO2013188771A3

  公开（公告）日：2014-02-20