Nickel(0)/Dihydroimidazol-2-ylidene Complex Catalyzed Coupling of Aryl Chlorides and Amines

Abstract

A general and simple nickel-catalyzed coupling of aryl chlorides and amines is reported. The scope and limitations of the coupling process using Ni(0), 1,3-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene, and NaO-t-Bu as base were investigated. Secondary cyclic and acyclic amines and anilines provided the arylamine coupling products in good to excellent yields. Compared to palladium-catalyzed aminations, this procedure offers an alternative route to N-substituted anilines starting from readily available aryl chlorides.

Smiles rearrangement for the synthesis of diarylamines

“…Physical and spectral data (mp, 1 H and 13 C NMR) of 3a were in agreement with the structure. 20 The scope and electronic effect of the present method were examined using a variety of substituted phenols and anilines. As shown in Table 1, m-and p-cresol, p-nitrophenol, and phydroxybenzaldehyde, and aniline, p-methoxyaniline, o-, m-, p-toluidine, p-nitroaniline were well tolerated in this reaction.…”

The coupling of carbon dioxide with ethene to produce acrylic acid sodium salt in one pot by using Ni(II) and Pd(II)-phosphine complexes as precatalysts

“…Nevertheless the in situ generation of Ni(0) species starting from Ni(II) complexes are frequently used in catalysis usually in the presence of reducing agents such as organometallic species [60][61][62][63][64][65][66][67] or Zn dust [28,49]. As a matter of facts, in the present case, according to Fig.…”

Transition Metal-Catalyzed Reactions Using N-Heterocyclic Carbene Ligands (Besides Pd- and Ru-Catalyzed Reactions)

“…Fort and coworkers have found that in situ generation of the Ni(0) and SIPr carbene efficiently catalyzes the coupling of aryl chlorides with various amines (Eq. 24) [58,59]. During the course of the study, it was discovered that Ni(0) could be generated from Ni(acac) 2 in the presence of NaH and t-BuOH.…”