[2,6-D2]benzoyl[2,6-D2]aniline

• 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: [2,6-D2]benzoyl[2,6-D2]aniline
• 英文别名: [2,6,2',6'-D4]benzanilide；benzanilide；2,6-dideuterio-N-(2,6-dideuteriophenyl)benzamide
• 化学式: C₁₃H₁₁NO
• 分子量: 201.205
• InChiKey: ZVSKZLHKADLHSD-ULDPCNCHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  [2,6-D2]benzoyl[2,6-D2]aniline 在 [(COD)Ir(dimethylphenylphosphine)(1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene)]PF₆ 、 氢气 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成
  参考文献：
  名称：

  高活性铱（I）配合物的合成及其在催化氢同位素交换中的应用

  摘要：

  AbstractA series of robust iridium(I) complexes bearing a sterically encumbered N‐heterocyclic carbene ligand, alongside a phosphine ligand, has been synthesised and investigated in hydrogen isotope exchange processes. These complexes have allowed isotope incorporation over a range of substrates with the use of practically convenient deuterium and tritium gas. Moreover, these active catalysts are capable of isotope incorporation to particularly high levels, whilst employing low catalyst loadings and in short reaction times. In addition to this, these new catalyst species have shown flexible levels of chemoselectivity, which can be altered by simple manipulation of preparative approaches. Furthermore, a number of industrially‐relevant drug molecules has also been labelled, including the sulfonamide containing drug, Celecoxib. Alongside detailed NMR experiments, initial mechanistic investigations have also been performed, providing insight into both substrate binding energies, and, more importantly, relative energies of key steps in the mechanistic cycle as part of the overall exchange process.magnified image

  DOI：

  10.1002/adsc.201400730
• 作为产物：
  描述：

  N-苯甲酰替苯胺 在 [{μ-(IDipp)PH}{Ir(cod)}₂{μ-Cl}][BAr^F₄] 、 氘 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 16.0h， 以100%的产率得到[2,6-D2]benzoyl[2,6-D2]aniline
  参考文献：
  名称：

  阳离子铱(I) NHC-亚膦配合物及其在氢同位素交换反应中的应用

  摘要：

  阳离子 Ir(I) NHC-膦亚胺配合物已在与各种芳族底物的 H/D 交换反应中进行了测试。该催化剂显示出与已报道和已建立的阳离子克尔型 HIE 催化剂相似的催化活性水平。

  DOI：

  10.1002/ejic.202200148

文献信息

• Application of neutral iridium(I)<i>N</i>-heterocyclic carbene complexes in<i>ortho</i>-directed hydrogen isotope exchange
  作者：Alison R. Cochrane、Stephanie Irvine、William J. Kerr、Marc Reid、Shalini Andersson、Göran N. Nilsson

  DOI：10.1002/jlcr.3084

  日期：2013.7

  Bench-stable complexes of the type [Ir(COD)(NHC)Cl] (NHC = N-heterocyclic carbene) have been investigated within the field of hydrogen isotope exchange. By employing a sterically encumbered NHC within such complexes and catalyst loadings of only 5 mol%, moderate to high deuterium incorporations were achieved across a range of aromatic ketones and nitrogen-based heterocycles. The simple and synthetically

  [Ir(COD)(NHC)Cl] (NHC = N-杂环卡宾) 类型的台式稳定配合物已在氢同位素交换领域进行了研究。通过在此类配合物中使用空间位阻 NHC，并且催化剂负载仅为 5 mol%，在一系列芳香酮和氮基杂环中实现了中到高的氘掺入。本文报道的简单且可合成的催化剂提供了基于膦的物种的替代品，并增加了与已建立的基于铱的同位素交换方法相关的可用标记系统。
• Iridium-Catalyzed H/D Exchange: Ligand Complexes with Improved Efficiency and Scope
  作者：Michael Parmentier、Thomas Hartung、Andreas Pfaltz、Dieter Muri

  DOI：10.1002/chem.201402078

  日期：2014.9.1

  could be labeled efficiently. With the addition of tris(pentafluorophenyl) borane to the reaction mixture, also highly deactivating nitrile substituents were well tolerated in the reaction. Based on the excellent results obtained with the chiral ThrePhox ligand, a structurally simpler, achiral ligand was developed. The iridium complex containing this ligand, proved to be a powerful catalyst for HIE reactions

  氢同位素交换（HIE）是将氘或tri引入有机化合物的最有吸引力的工具之一。在此，已对具有N，P-配体的铱络合物（用于不对称双键还原的高活性催化剂）的HIE功能进行了测试。含有二环己基膦或次膦酸酯的富电子配体被认为是有效掺入氘的优异配体。具有强指导基团（即吡啶，酮和酰胺）以及弱连接单元（如硝基，砜和磺酰胺）的底物可以得到有效标记。通过向反应混合物中加入三（五氟苯基）硼烷，在反应中也很好地耐受了高度失活的腈取代基。基于使用手性ThrePhox配体获得的优异结果，开发了结构更简单的非手性配体。含有该配体的铱络合物被证明是HIE反应的有力催化剂。
• Highly active iridium(i) complexes for catalytic hydrogen isotope exchange
  作者：Jack A. Brown、Stephanie Irvine、Alan R. Kennedy、William J. Kerr、Shalini Andersson、Göran N. Nilsson

  DOI：10.1039/b715938b

  日期：——

  Practically convenient methods have been developed for the preparation of new iridium complexes, possessing bulky N-heterocyclic carbene and phosphine ligands; these routinely handled complexes are highly active catalysts within directed hydrogen isotope exchange processes.

  已经开发出了用于制备具有庞大的N-杂环卡宾和膦配体的新型铱配合物的实用方便的方法。这些常规处理的配合物是定向氢同位素交换过程中的高活性催化剂。
• Practically convenient and industrially-aligned methods for iridium-catalysed hydrogen isotope exchange processes
  作者：A. R. Cochrane、C. Idziak、W. J. Kerr、B. Mondal、L. C. Paterson、T. Tuttle、S. Andersson、G. N. Nilsson

  DOI：10.1039/c4ob00465e

  日期：——

  The use of alternative solvents in the iridium-catalysed hydrogen isotope exchange reaction with developing phosphine/NHC Ir(i) complexes has identified reaction media which are more widely applicable than the commonly employed chlorinated solvent, dichloromethane.

  在使用磷胺/NHC Ir(i)配合物进行铱催化的氢同位素交换反应中，使用替代溶剂已确定比常用的氯代溶剂二氯甲烷更广泛适用的反应介质。
• Application of iridium pincer complexes in hydrogen isotope exchange reactions
  作者：Annika Träff、Göran N. Nilsson、Kálmán J. Szabó、Ludvig Eriksson

  DOI：10.1016/j.jorganchem.2007.09.009

  日期：2007.12

  Iridium pincer complex catalyzed hydrogen to deuterium exchange could be achieved using aromatic and heteroaromatic substrates. The reactions proceed under mild conditions and with high regioselectivity. The efficiency of the hydrogen isotope exchange reaction depends on the electronic properties of the pincer complex catalyst.

  使用芳族和杂芳族底物可以实现铱螯合剂催化氢与氘的交换。反应在温和条件下和高区域选择性下进行。氢同位素交换反应的效率取决于夹钳复合催化剂的电子性质。