2'-methoxy-N,N-dimethyl-[1,1'-biphenyl]-4-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: 2'-methoxy-N,N-dimethyl-[1,1'-biphenyl]-4-amine
• 英文别名: 2′-methoxy-N,N-dimethylbiphenyl-4-amine；4'-(N,N-dimethylamino)-2-methoxybiphenyl；4-(2-methoxyphenyl)-N,N-dimethylaniline；(2'-methoxybiphenyl-4-yl)dimethylamine
• 化学式: C₁₅H₁₇NO
• 分子量: 227.306
• InChiKey: ZULAWKQYMWDGQJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2'-methoxy-N,N-dimethyl-[1,1'-biphenyl]-4-amine 、 对甲苯基溴化镁 在 [bis(tributylphosphine)nickeldichloride] 作用下， 以 2-甲基四氢呋喃 、 乙醚 为溶剂， 反应 40.0h， 以40%的产率得到
  参考文献：
  名称：

  受阻较少的配体为镍催化芳族醚的格利雅交联提供了改进的催化剂†

  摘要：

  已经发现，使用空间位阻较少的配体的镍配合物可以最有效地催化未活化的邻位取代的芳族醚与格氏试剂的挑战性反应。空气稳定，廉价，可商购的[NiCl 2（P n Bu 3）2 ]是这类转化的改进催化剂。当在更高的温度和低至0.1摩尔％的催化剂负载下进行检查时，这种催化剂的改进结果甚至可以扩展到活化程度更高的底物的某些偶联。在后面这些反应中异常的诱导期与充当助催化剂的副产物镁盐有关。

  DOI：

  10.1039/c7cy01205e
• 作为产物：
  描述：

  2-氯苯甲醚 、 4-(N,N-二甲基)苯胺溴化镁 在 C₃₅H₃₁BrN₄NiP 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以72%的产率得到2'-methoxy-N,N-dimethyl-[1,1'-biphenyl]-4-amine
  参考文献：
  名称：

  Cross-Coupling of ArX with ArMgBr Catalyzed by N-Heterocyclic Carbene-Based Nickel Complexes

  摘要：

  N-Heterocyclic carbene-based pincer nickel complexes were synthesized and characterized. These complexes efficiently catalyze cross-coupling of aryl Grignard reagents with aryl chlorides or fluorides under mild conditions.

  DOI：

  10.1021/jo302425x

文献信息

• [Pd(Cl)2{P(NC5H10)(C6H11)2}2]-A Highly Effective and Extremely Versatile Palladium-Based Negishi Catalyst that Efficiently and Reliably Operates at Low Catalyst Loadings
  作者：Jeanne L. Bolliger、Christian M. Frech

  DOI：10.1002/chem.201001201

  日期：——

  electronically activated, non‐activated, deactivated, sterically hindered, heterocyclic, and functionalized aryl bromides with various (also heterocyclic) arylzinc reagents, typically within a few minutes at 100 °C in the presence of just 0.01 mol % of catalyst. Aryl bromides containing nitro, nitrile, ether, ester, hydroxy, carbonyl, and carboxyl groups, as well as acetals, lactones, amides, anilines,

  [Pd（Cl）2 P（NC 5 H 10）（C 6 H 11）2 } 2 ]（1）已通过使市售的[Pd（cod）（Cl）2 ]反应定量制备。室温下在几分钟内在N 2中与易于制备的1-（二环己基膦酰基）哌啶在甲苯中的环辛二烯）。综合大楼1已被证明是极佳的Negishi催化剂，能够将各种电子活化，非活化，失活，空间受阻，杂环和官能化的芳基溴化物与各种（也是杂环的）芳基锌试剂定量偶联，通常在几分钟内即可完成。 100°C，仅存在0.01 mol％的催化剂。含有硝基，腈，醚，酯，羟基，羰基和羧基的芳基溴化物，以及缩醛，内酯，酰胺，苯胺，烯烃，羧酸，乙酸，吡啶和嘧啶已被成功用作偶联伙伴。此外，在两个反应伙伴中都可以容忍电子和空间变化。实验观察强烈表明分子机制是有效的。
• <i>t</i>BuLi-Mediated One-Pot Direct Highly Selective Cross-Coupling of Two Distinct Aryl Bromides
  作者：Carlos Vila、Sara Cembellín、Valentín Hornillos、Massimo Giannerini、Martín Fañanás-Mastral、Ben L. Feringa

  DOI：10.1002/chem.201502709

  日期：2015.10.26

  A Pd‐catalyzed direct cross‐coupling of two distinct aryl bromides mediated by tBuLi is described. The use of [Pd‐PEPPSI‐IPr] or [Pd‐PEPPSI‐IPent] as catalyst allows for the efficient one‐pot synthesis of unsymmetrical biaryls at room temperature. The key for this selective cross‐coupling is the use of an ortho‐substituted bromide that undergoes lithium–halogen exchange preferentially.

  描述了由t BuLi介导的 Pd 催化的两种不同芳基溴化物的直接交叉偶联。使用 [Pd-PEPPSI-IPr] 或 [Pd-PEPPSI-IPent] 作为催化剂，可以在室温下有效地单锅合成不对称联芳基化合物。这种选择性交叉偶联的关键是使用优先进行锂-卤素交换的邻位取代溴化物。
• Acyclic diaminocarbenes: simple, versatile ligands for cross-coupling reactions
  作者：Bhartesh Dhudshia、Avinash N. Thadani

  DOI：10.1039/b516398f

  日期：——

  Acyclic diaminocarbenes are found to be useful ligands for palladium catalyzed Suzuki–Miyaura, Sonogashira and Heck cross-coupling reactions of aryl/alkenyl bromides and chlorides.

  发现非环状二胺卡宾在钯催化的铃木-宫浦反应、草贺桥（Sonogashira）反应和赫克反应中对芳基/烯基溴化物和氯化物作为有效配体。
• Unsymmetrical biaryl synthesis: An approach to natural highly functionalised biaryls via palladium catalysed coupling
  作者：David A. Widdowson、Ying-Zhi Zhang

  DOI：10.1016/s0040-4020(01)87628-6

  日期：1986.1

  The synthetic utility of the palladium catalysed cross-coupling reaction of aryl iodides and bromides with aryl Grignard reagents has been explored with respect to the polyoxygenated and polyalkylated arenes found in nature. High yields of unsymmetrical biaryls are obtained, free of symmetrical byproducts. The method will tolerate a limit of two -substituents in the biaryl system with a preference

  关于在自然界中发现的多加氧和多烷基化的芳烃，已经研究了芳基碘化物和溴化物与芳基格利雅试剂的钯催化交叉偶联反应的合成实用性。获得高收率的不对称联芳基，不含对称副产物。该方法将容许在联芳基系统中限制两个取代基，优选两个基团在芳基镁环上。关于该偏好讨论了潜在速率确定步骤的过渡状态模型。
• Mono- and Dinuclear Pincer Nickel Catalyzed Activation and Transformation of C–Cl, C–N, and C–O Bonds
  作者：Xia Yang、Zhong-Xia Wang

  DOI：10.1021/om500452c

  日期：2014.10.27

  Condensation of 2-NH2C6H4P(Et)Ph (2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2'-CH-N)C6H4P(Et)Ph (3). Treatment of 3 with NaH and followed by (DME)NiX2 (X = Cl, Br) afforded mononuclear pincer nickel complexes [Ni2-(C4H3N-2'-CH-N)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)](2)(CH2)(n) (5a, n = 3; 5b, n = 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2'-CH-N)C6H4P(Ph)](2)(CH2)(n) (6a, n = 3; 6b, n = 4) and [2-(5'-tBuC(4)H(3)N-2'-CH-N)C6H4P(Ph)](2)(CH2)(4) (6c). Respective treatment of 6ac with NaH followed by (DME)NiX2 (X = Cl, Br) gave the dinuclear nickel complexes [Ni2-(5'-RC4H2N-2'-CH-N)C6H4P(Ph)}X](2)(CH2)(n) (7a, R = H, X = Cl, n = 3; 7b, R = H, X = Cl, n = 4; 7c, R = H, X = Br, n = 4; 7d, R = tBu, X = Cl, n = 4). Catalysis of the complexes for the activation and transformation of CCl, CN, and CO bonds was evaluated. Complex 7c exhibited excellent catalytic activity in the cross-coupling of aryl chlorides or aryltrimethylammonium iodides with arylzinc reagents as well as of aryl sulfamates with aryl Grignard reagents. The dinuclear nickel complexes 7bd showed higher catalytic activity than the mononuclear complexes in each type of reaction.