5-bromo-4'-methoxybiphenyl-2-amine

• 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: 5-bromo-4'-methoxybiphenyl-2-amine
• 英文别名: 5-bromo-4'-methoxy-(1,1'-biphenyl)-2-amine；4-Bromo-2-(4-methoxyphenyl)aniline
• 化学式: C₁₃H₁₂BrNO
• 分子量: 278.148
• InChiKey: GXBMDJKPAMBYKU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  35.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,4-二溴苯胺 、 4-甲氧基苯基溴化镁 在 tris-(dibenzylideneacetone)dipalladium(0) 、 C₃₀H₂₃O₂P 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到5-bromo-4'-methoxybiphenyl-2-amine
  参考文献：
  名称：

  DHTP配体用于双卤代芳烃与格利雅试剂的高邻位选择性，钯催化交叉偶联：改进构象的方法

  摘要：

  据报道，带有二羟基三苯膦配体（如1）的钯催化剂可用于格氏试剂和二卤代芳烃的邻位选择性交叉偶联。三苯基膦配体上的第二个羟基大大提高了催化效率并扩大了反应范围。

  DOI：

  10.1002/anie.200905544

文献信息

• DHTP Ligands for the Highly Ortho-Selective, Palladium-Catalyzed Cross-Coupling of Dihaloarenes with Grignard Reagents: A Conformational Approach for Catalyst Improvement
  作者：Shunpei Ishikawa、Kei Manabe

  DOI：10.1002/anie.200905544

  日期：2010.1.18

  Palladium catalysts bearing dihydroxyterphenylphosphine ligands (such as 1) are reported for the ortho‐selective cross‐coupling of Grignard reagents and dihaloarenes. The second hydroxy group onto the terphenylphosphine ligand dramatically improved the catalytic efficiency and expanded the scope of the reaction.

  据报道，带有二羟基三苯膦配体（如1）的钯催化剂可用于格氏试剂和二卤代芳烃的邻位选择性交叉偶联。三苯基膦配体上的第二个羟基大大提高了催化效率并扩大了反应范围。
• Cobalt-Catalyzed Biaryl Couplings via C–F Bond Activation in the Absence of Phosphine or NHC Ligands
  作者：Juan Wei、Kun-Ming Liu、Xin-Fang Duan

  DOI：10.1021/acs.joc.6b02354

  日期：2017.2.3

  Co-catalyzed biaryl coupling through C–F cleavage under phosphine or NHC-free conditions was described. A broad range of aryl fluorides including unactivated fluorides as well as those with sensitive functionalities could couple with various Ti(OEt)4-mediated aryl Grignard reagents with high selectivity under the catalysis of CoCl2/DMPU. Importantly, selective C–F bond activation couplings between two types

  描述了在膦或无NHC的条件下通过CF裂解产生的高度通用的选择性Co催化联芳基偶合。在CoCl 2 / DMPU的催化下，包括未活化的氟化物以及具有敏感功能的芳基氟化物在内的各种芳基氟化物都可以与各种Ti（OEt）4介导的芳基格利雅试剂进行高选择性的偶联。重要的是，还可以实现两种类型的氟之间的选择性CF键活化偶联（二氟芳族化合物和两个不同的偶联配偶体），并且在存在CCl或CBr键的情况下也可以实现。
• Ortho-selective Cross Coupling of Dibromophenols and Dibromoanilines with Grignard Reagents in the Presence of Palladium Catalysts Bearing Hydroxylated Oligoarene-type Phosphine
  作者：Shunpei Ishikawa、Kei Manabe

  DOI：10.1246/cl.2007.1304

  日期：2007.11.5

  p-Terphenylphosphines with a hydroxy group were used as ligands for palladium in the catalytic cross coupling of dibromophenols and dibromoanilines with Grignard reagents. High ortho-selectivity that cannot be achieved with other phosphine ligands was observed.

  具有羟基的对联苯基膦被用作钯的配体，在二溴酚和二溴苯胺与格里尼亚反应试剂的催化交叉偶联中使用。观察到其他膦配体无法实现的高邻位选择性。
• Synthesis of Substituted Monohalobenzenes via Ortho-Selective Cross-Coupling of Dihalobenzenes with Electron-Donating Ortho-Directing Groups
  作者：Kei Manabe、Shunpei Ishikawa

  DOI：10.1055/s-2008-1067270

  日期：2008.10

  Dihalobenzenes that possess directing groups such as OH, CH 2 OH, NH 2 , NHAc, or NHBoc were subjected to ortho-selective cross-coupling with Grignard reagents in the presence of palladium-based catalysts to give the corresponding substituted monohalobenzenes. For the dibromo- and dichlorophenols and anilines, hydroxylated terphenylphosphines 1 and 2 were found to be effective ligands for palladium

  在钯基催化剂存在下，将具有导向基团如 OH、CH 2 OH、NH 2 、NHAc 或 NHBoc 的二卤代苯与格氏试剂进行邻位选择性交叉偶联，得到相应的取代单卤代苯。对于二溴和二氯苯酚和苯胺，羟基化三联苯膦 1 和 2 被发现是钯的有效配体，而三环己基膦对于二氯苯甲醇、二氯苯胺和二氟苯来说是优选的。
• Hydroxylated terphenylphosphine ligands for palladium-catalyzed ortho-selective cross-coupling of dibromophenols, dibromoanilines, and their congeners with Grignard reagents
  作者：Shunpei Ishikawa、Kei Manabe

  DOI：10.1016/j.tet.2011.09.013

  日期：2011.12

  p-Terphenylphosphines bearing one or two hydroxy groups were used as ligands to palladium in the cross-coupling of dibromophenols, dibromoanilines, and their congeners with Grignard reagents. High ortho-selectivity that cannot be achieved using other phosphine ligands was observed. ortho-Preference was also observed in competitive cross-coupling reactions of two substrates. A significant effect of the concentration of the Grignard reagent on the ortho-selectivity was observed, when the hydroxylated terphenylphosphines were used. Kinetic studies on this effect showed that high concentrations of the Grignard reagent retard the cross-coupling reaction only at the para-position, but not at the ortho-position. (C) 2011 Elsevier Ltd. All rights reserved.