C–N Cross-coupling Reactions of Amines with Aryl Halides Using Amide-Based Pincer Nickel(II) Catalyst

Highly economical and direct amination of sp3 carbon using low-cost nickel pincer catalyst

“…In the presence of a base, the amine is likely to reduce 1 to 2aa, removing the labile Cl − . 63 Upon oxidative addition, toluene is substituted, producing 2ab. We hypothesize that the toluene is then oxidized to the aldehyde in the presence of DMSO.…”

Advances in Cross-Coupling Reactions Catalyzed by Aromatic Pincer Complexes Based on Earth-Abundant 3d Metals (Mn, Fe, Co, Ni, Cu)

“…The Ullmann reaction (Scheme 7a) was the first reported C-N coupling, which employs stoichiometric amounts of copper salts for the activation of aryl halides that react with amine nucleophiles. Despite its great versatility, the stoichiometric generation of copper salts as a residue and the harsh conditions required represent the main problems in this reaction [97]. On the other hand, the Buchwald-Hartwig coupling (Scheme 7b) employs palladium complexes as catalysts with conditions that are much milder compared to Ullmann couplings [93].…”

Nickel‐Catalysed Amination of Arenes and Heteroarenes

“…The first time usage of a Nickel pincer-based catalyst in the coupling of aryl halides and amines was reported to synthesize diverse CÀ N cross coupled adducts. [33] The catalytic system stands superior being stable and effective with low catalyst loadings under simple reaction in short reaction times. With the Ni catalyst, the cross coupling of varied aryl halides with both 1°and 2°amines was performed in presence of a base in DMSO which afforded considerable yields of the products (Scheme 10).…”

“…The first time usage of a Nickel pincer‐based catalyst in the coupling of aryl halides and amines was reported to synthesize diverse C−N cross coupled adducts [33] . The catalytic system stands superior being stable and effective with low catalyst loadings under simple reaction in short reaction times.…”