Suzuki-type coupling of chloroarenes with arylboronic acids catalysed by nickel complexes

Palladium/Phosphite Catalyst Systems for Efficient Cross Coupling of Aryl Bromides and Chlorides with Phenylboronic Acid

“…Due to the industrial interest in the functionalization of economically attractive aryl chlorides [7] there is currently a great deal of interest in the coupling of aryl chlorides with arylboronic acids. While Indolese [8] and Saito et al [9] demonstrated that nickel catalysts are useful for this purpose, most studies focussed on palladium catalysts. After initial work by us, [10] and others, [11] Fu, [12] Buchwald, [13] and Nolan [14] recently developed significant breakthroughs in this area.…”

Nickel-promoted ligand-free palladium-catalyzed Suzuki coupling reaction

“…In particular, using NiCl 2 and NiSO 4 as the additives, the reaction gave near quantitative yield of the product. No reaction was observed when only Ni(II)/PVP was added under these reaction conditions, although in the presence of some ligands Ni(II) can catalyze the Suzuki coupling [30,31]. The synergistic effect of Pd/Ni is obvious.…”

Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

“…The group of Fort [28] developed Ni-carbene complexes for the amination of aryl chlorides and Buchwald [29] successfully applied Cu complexes as catalysts for the amination and amidation of aryl chlorides under relatively mild conditions. [11] After a systematic screening of mono-and diphosphine ligands, solvents and various bases, a NiCl 2 dppf complex was found to be the best catalyst giving good to very high yields for a variety of substituted coupling partners (see Figure 12). Catalyst loadings as low as 0.5% were possible for activated aryl chlorides, for less reactive coupling partners 3 -10% were necessary at a reaction time of 16 hours.…”

“…1985 Development of first industrial processes (selected milestones see below) [7,10] 1995 Ni catalysts for Suzuki coupling developed [11] 1998 Catalysts for the activation of aryl chlorides for Heck, Suzuki, Buchwald-Hartwig amination etc. ; secondary phosphines; palladacycles -secondary phosphines [13,14] 1998 Systematic investigation of the carbonylation of aryl halides; carbonylation of (hetero) aryl chlorides [10,15] When discussing absolute figures, one should always keep in mind that these can vary broadly depending on the situation for a specific process development.…”