N-(4-bromophenyl)-P,P-diphenylphosphinic amide | 101318-12-1

• 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: N-(4-bromophenyl)-P,P-diphenylphosphinic amide
• 英文别名: P,P-diphenyl-N-(4-bromophenyl) phosphinic amide；N-diphenylphosphoryl-4-bromoaniline, C~18~H~15~BrNOP；4-bromo-N-diphenylphosphorylaniline
• CAS: 101318-12-1
• 化学式: C₁₈H₁₅BrNOP
• 分子量: 372.201
• InChiKey: GCSUDOQBYLHDGE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• 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：
  2

反应信息

• 作为反应物：
  描述：

  N-(4-bromophenyl)-P,P-diphenylphosphinic amide 、 4,5-dimethyl-2-(trimethylsilyl)phenyl triflate 在 potassium fluoride 、 18-冠醚-6 、 caesium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以57%的产率得到N-(4-bromophenyl)-2-(diphenylphosphoryl)-4,5-dimethylaniline
  参考文献：
  名称：

  Insertion of Arynes into Arylphosphoryl Amide Bonds: One-Step Simultaneous Construction of C–N and C–P Bonds

  摘要：

  The insertion of arynes into arylphosphoryl amide bonds to synchronously construct C-P and C-N bonds is described. Arynes generated in situ from o-triflate arylsilanes under fluoride-promoted conditions insert into relatively inert P-N bonds, producing o-amine-substituted arylphosphine oxides. This process provides a simple pathway for the preparation of precursors for a number of bidentate aminophosphine ligands.

  DOI：

  10.1021/ol402748u
• 作为产物：
  描述：

  4-溴苯胺 、 二苯基次膦酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以79%的产率得到N-(4-bromophenyl)-P,P-diphenylphosphinic amide
  参考文献：
  名称：

  Insertion of Arynes into Arylphosphoryl Amide Bonds: One-Step Simultaneous Construction of C–N and C–P Bonds

  摘要：

  The insertion of arynes into arylphosphoryl amide bonds to synchronously construct C-P and C-N bonds is described. Arynes generated in situ from o-triflate arylsilanes under fluoride-promoted conditions insert into relatively inert P-N bonds, producing o-amine-substituted arylphosphine oxides. This process provides a simple pathway for the preparation of precursors for a number of bidentate aminophosphine ligands.

  DOI：

  10.1021/ol402748u

文献信息

• Redox-Neutral P(O)–N Coupling between P(O)–H Compounds and Azides via Dual Copper and Photoredox Catalysis
  作者：Yanan Wu、Ken Chen、Xia Ge、Panpan Ma、Zhiyuan Xu、Hongjian Lu、Guigen Li

  DOI：10.1021/acs.orglett.0c02207

  日期：2020.8.7

  We report a redox-neutral P(O)–N coupling reaction of P(O)–H compounds with azides via photoredox and copper catalysis, providing new access to useful phosphinamides, phosphonamides, and phosphoramides. This transformation tolerates a wide range of nucleophilic functionalities including alcohol and amine nucleophiles, which makes up for the deficiency of classical nitrogen nucleophilic substitution

  我们报道了P（O）-H化合物与叠氮化物通过光氧化还原和铜催化的氧化还原中性P（O）-N偶联反应，提供了获得有用的次膦酰胺，膦酰胺和磷酰胺的新途径。这种转化可耐受多种亲核功能，包括醇和胺亲核，这弥补了传统氮亲核取代反应的不足。为了证明这种新方法的广泛潜在应用，已开发了多种含叠氮基天然产物和药物分子的后期功能化，初步的不对称反应和连续的可见光光流过程。
• Practical Synthesis of Phosphinic Amides/Phosphoramidates through Catalytic Oxidative Coupling of Amines and P(O)−H Compounds
  作者：Chen Tan、Xinyuan Liu、Huanxin Jia、Xiaowen Zhao、Jian Chen、Zhiyong Wang、Jiajing Tan

  DOI：10.1002/chem.201904237

  日期：2020.1.16

  Herein, we report a highly efficient ZnI2 -triggered oxidative cross-coupling reaction of P(O)-H compounds and amines. This operationally simple protocol provides unprecedented generic access to phosphinic amides/phosphoramidate derivatives in good yields and short reaction time. Besides, the reaction proceeds under mild conditions, which avoids the use of hazardous reagents, and is applicable to scale-up

  在本文中，我们报告了P​​（O）-H化合物与胺类的高效ZnI2触发的氧化交叉偶联反应。该操作简单的方案以高收率和较短的反应时间提供了对次膦酰胺/氨基磷酸酯衍生物的空前通用访问。此外，该反应在温和的条件下进行，避免了使用有害试剂，并且适用于按比例放大的合成以及药物分子的后期功能化。立体特异性偶联也可以从容易获得的光学富集的P（O）-H化合物中获得。
• Ligand-free copper-catalyzed denitrogenative arylation of phosphorylamides with arylhydrazines
  作者：Qiao Zhu、Shiying Che、Zhenghong Luo、Zijian Zhao

  DOI：10.1080/00397911.2020.1725577

  日期：2020.4.2

  Abstract A straightforward arylation of phosphorylamides with arylhydrazines hydrochloride was herein demonstrated. The protocol proceeded in the presence of a catalytic loading of Cu(OAc)2 as the catalyst, DTBP as the external oxidant and Cs2CO3 as the base, but without any ligands. And a series of N-aryl phosphorylamides were successfully obtained in high efficiency (up to 93% yields) with good substituents

  摘要 本文证明了磷酰胺与芳基肼盐酸盐的直接芳基化反应。该协议在 Cu(OAc)2 作为催化剂、DTBP 作为外部氧化剂和 Cs2CO3 作为碱的催化负载存在下进行，但没有任何配体。并且成功地获得了一系列N-芳基磷酰胺，其具有良好的取代基相容性（多达30个例子），具有高效率（高达93％的产率）。基于控制反应和文献探索的结果，提出了自由基机理的简便方法。图形概要
• The Chan-Evans-Lam N -arylation of phosphonic/phosphinic amides
  作者：Yuqin Xu、Qiong Su、Wanrong Dong、Zhihong Peng、Delie An

  DOI：10.1016/j.tet.2017.06.028

  日期：2017.8

  A stoichiometric copper(II)-mediated arylation protocol of phosphinamides and phosphonamides was herein demonstrated. Various unreported N-aryl phosphinamides and phosphonamides were successfully prepared through Chan-Evans-Lam reaction with high efficiency (up to 88% yields) and good functional groups tolerance (30 examples) in the absence of any ligands or co-catalysts.

  本文证明了化学计量的铜（II）介导的次膦酰胺和膦酰胺的芳基化方案。在没有任何配体或助催化剂的情况下，通过Chan-Evans-Lam反应以高效率（高达88％的收率）和良好的官能团耐受性（30个实例）成功地制备了各种未报告的N-芳基次膦酰胺和膦酰胺。
• Metallaphotoredox-Enabled Construction of the P(O)–N Bond from Aromatic Amines and P(O)–H Compounds
  作者：Kai-Cheng Yu、Hai Li、Yuan-Hong Tu、Hui Zhao、Xiang-Guo Hu

  DOI：10.1021/acs.orglett.2c03860

  日期：2022.12.16

  We have developed a dual copper/photoredox-catalyzed approach for the construction of the P(O)–N bond from commercially available aromatic amines and P(O)–H compounds. This metallaphotoredox method avoids toxic or corrosive reagents and does not require prefunctionalized substrates. The reaction has a broad substrate scope and is suitable for the synthesis of phosphonamides and phosphinamides, thus

  我们开发了一种双铜/光氧化还原催化方法，用于从市售芳香胺和 P(O)-H 化合物构建 P(O)-N 键。这种金属光氧化还原方法避免了有毒或腐蚀性试剂，并且不需要预功能化的底物。该反应具有广泛的底物范围，适用于膦酰胺和膦酰胺的合成，从而补充了以前的非光化学方法。该反应适用于药物分子的直接修饰，并且可以在克规模上进行。