3,5-bis(trifluoromethyl)-N-(1-phenylethyl)benzenamine

• 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: 3,5-bis(trifluoromethyl)-N-(1-phenylethyl)benzenamine
• 英文别名: N-(1-phenylethyl)-3,5-bis(trifluoromethyl)aniline；N-1-phenylethyl-3,5-bis(trifluoromethyl)aniline
• 化学式: C₁₆H₁₃F₆N
• 分子量: 333.276
• InChiKey: NHXAVQASYGVNDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  间二(三氟甲基)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 3,5-bis(trifluoromethyl)-N-(1-phenylethyl)benzenamine
  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

• An Effective [Fe^III(TF₄DMAP)Cl] Catalyst for C–H Bond Amination with Aryl and Alkyl Azides
  作者：Yi-Dan Du、Zhen-Jiang Xu、Cong-Ying Zhou、Chi-Ming Che

  DOI：10.1021/acs.orglett.8b03765

  日期：2019.2.15

  [FeIII(TF4DMAP)Cl] can efficiently catalyze intermolecular sp3 C–H amination using aryl azides and intramolecular sp3 C–H amination of alkyl azides in moderate-to-high product yields. At catalyst loading down to 1 mol %, the reactions display high chemo- and regioselectivity with broad substrate scope and are effective for late-stage functionalization of complex natural/bioactive molecules.

  的[Fe III（TF 4 DMAP）CL]可以有效地催化分子间的SP 3 C-H使用芳基叠氮化和分子内藻胺化3烷基叠氮化物的C-H的胺化在中度到高的产物收率。在低至1 mol％的催化剂负载量下，反应显示出高的化学选择性和区域选择性以及广泛的底物范围，并且对于复杂的天然/生物活性分子的后期功能化有效。
• Enantioselective Hydrogenation of Acyclic Aromatic <i>N</i>-Aryl Imines Catalyzed by an Iridium Complex of (<i>S,S</i>)-1,2-Bis(<i>tert</i>-butylmethylphosphino)ethane
  作者：Tsuneo Imamoto、Noriyuki Iwadate、Kazuhiro Yoshida

  DOI：10.1021/ol060546b

  日期：2006.5.1

  [reaction: see text] An iridium(I) complex of (S,S)-1,2-bis(tert-butylmethylphosphino)ethane with tetrakis(3,5-bis(trifluoromethyl)phenyl)borate as the counterion catalyzes the hydrogenation of acyclic aromatic N-aryl imines under 1 atm of hydrogen pressure at room temperature to give the corresponding optically active secondary amines with up to 99% ee.

  [反应：参见正文]（S，S）-1,2-双（叔丁基甲基膦基）乙烷与四（3,5-双（三氟甲基）苯基）硼酸酯的铱（I）络合物作为抗衡离子催化加氢反应在室温下，在1个大气压的氢气压力下，在室温下制备无环芳族N-芳基亚胺，得到相应的旋光仲胺，其ee高达99％。
• Iron porphyrin catalysed light driven C–H bond amination and alkene aziridination with organic azides
  作者：Yi-Dan Du、Cong-Ying Zhou、Wai-Pong To、Hai-Xu Wang、Chi-Ming Che

  DOI：10.1039/d0sc00784f

  日期：——

  strategy for the design of C–N bond formation reactions under mild reaction conditions, the challenge being lack of selectivity as a free nitrene reactive intermediate is usually involved. Herein is described an iron(III) porphyrin catalysed sp3 C–H amination and alkene aziridination with selectivity by using organic azides as the nitrogen source under blue LED light (469 nm) irradiation. The photochemical

  在温和的反应条件下，可见光驱动的有机叠氮化物的氮烯转移和插入反应是设计C–N键形成反应的一种有吸引力的策略，因为通常涉及游离的腈反应性中间体，因此缺乏选择性的挑战。本文描述了铁（III）卟啉催化的sp 3通过使用有机叠氮化物作为氮源，在蓝色LED光（469 nm）照射下，进行C–H胺化和烯烃的叠氮化。光化学反应显示化学选择性和区域选择性，并且对于复杂的天然和生物活性化合物的后期功能化有效。机理研究表明，卟啉铁既起光敏剂的作用，又起催化剂的作用，产生了反应性的铁-氮化物中间体，随后形成C-N键。
• On the Superior Activity of In(I) versus In(III) Cations Toward <i>ortho-C-</i>Alkylation of Anilines and Intramolecular Hydroamination of Alkenes
  作者：Zhilong Li、Shengwen Yang、Guillaume Thiery、Vincent Gandon、Christophe Bour

  DOI：10.1021/acs.joc.0c01585

  日期：2020.10.16

  ortho-C-alkylation of unprotected anilines with a variety of styrenes and alkenes using a univalent cationic indium(I) catalyst is reported. Mechanistic studies revealed that the reaction likely proceeds via a tandem hydroamination/Hofmann–Martius rearrangement. The high compatibility between the cationic indium(I) complex and primary anilines led us to develop an In(I)+-catalyzed hydroamination of alkenes

  一种有效的邻- Ç与各种使用一价阳离子铟苯乙烯和烯烃的未受保护的苯胺的烷基化报告（I）的催化剂。机理研究表明，该反应可能是通过串联加氢胺化/霍夫曼-马修斯重排而进行的。阳离子铟（I）配合物与伯苯胺之间的高度相容性使我们开发了使用未保护的伯和仲烯基胺进行In（I）+催化的烯烃加氢胺化反应。计算支持裸In（I）+离子的催化活性，并具有形成C–N键的外球机理和潜在的内球原金属化。
• Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility
  作者：Lei Xu、Yan-Ping Luo、Lin Sun、Yan Xu、Zhong-Sheng Cai、Min Fang、Rong-Xin Yuan、Hong-Bin Du

  DOI：10.1002/chem.201600447

  日期：2016.4.25

  The construction of highly stable metal–porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light‐harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal–porphyrinic framework (denoted as NUPF‐1) and its catalytic properties. NUPF‐1 is constructed from a new porphyrin

  高度稳定的金属-卟啉骨架（MPF）的构建吸引人，因为这些材料为在人工光收集系统，气体存储，多相催化等方面的应用提供了巨大的机会。在此，我们报道了一种新型的介孔金属-卟啉骨架的合成骨架（表示为NUPF-1）及其催化性能。NUPF-1从一个新的卟啉接头和Zr的构造6 ö 8结构的建筑物单元，具有前所未有的双重互穿SCU网。该结构不仅具有出色的化学和热稳定性，而且还具有独特的结构柔韧性，这在金属-有机骨架（MOF）材料中很少见到。由于具有高化学稳定性的优点，NUPF-1可以很容易地用[Ru 3（CO）12 ]进行后金属化，并且生成的NUPF-1-RuCO}具有催化活性，可作为分子间C（sp 3）的非均相催化剂）-H胺化。对于用各种有机叠氮化物胺化小的基材，已经实现了优异的产率和良好的可回收性。