Nickel catalysts Suzuki-Miyaura reaction

Inamoto and Doi have also worked on pincer-type biscarbene complexes of nickel(II). Pre-catalyst 20 was successfully applied to the Suzuki-Miyaura reaction... 

Other successful examples of catalysts containing NHC ligands are found in palladium- and nickel-catalyzed carbon-carbon bond formations. The catalyst development with these metals has focused in particular on Heck-type reactions, especially the Mizoroki-Heck reaction itself [Eq. (42)] and various cross coupling reactions [Eq. (43)], e.g., the Suzuki-Miyaura reaction ([M] = and the Kumada-Corriu reaction ([M] = MgBr). " Related reactions like the Sonogashira coupling [Eq. (44)]326-329 Buchwald-... 

The three basic steps in the palladium-catalysed Suzuki-Miyaura reaction involve oxidative addition, transmetalation, and reductive elimination. A systematic study of the transmetalation step has found that the major process involves the reaction of a palladium hydroxo complex with boronic acid, path B in Scheme 3, rather than the reaction of a palladium halide complex with trihydroxyborate, path A. A kinetic study using electrochemical techniques of Suzuki—Miyaura reactions in DMF has also emphasized the important function of hydroxide ions. These ions favour reaction by forming the reactive palladium hydroxo complex and also by promoting reductive elimination. However, their role is a compromise as they disfavour reaction by forming of unreactive anionic trihydroxyborate. A method for coupling arylboronic acids with aryl sulfonates or halides has been developed using a nickel-naphthyl complex as a pre-catalyst. It works at room temperature in toluene solvent in the presence of water and potassium carbonate. ... 

Reaction of (diisopropylamino)chloroboryl ethers of alkynols (57) with alkynyl-stannanes (58) in the presence of nickel catalysts has been reported to afford formal f/ms-alkynylboration products (60), which could undergo the Suzuki-Miyaura coupling with organic halides. The 2-borylalkenylnickel(II) complex (59) was isolated as an intermediate in a reaction of the chloroboryl ether (57) with 1 equiv. of a nickel(0)-phosphine complex and characterized by X-ray crystallography.61... 

Han has comprehensively reviewed the use of nickel catalysts for the Suzuki-Miyaura cross-coupling reaction/ and found that the nickel mediated process can tolerate a broad range of aryl electrophiles, for example, sulfamates, carbamates, carboxylates, ethers, carbonates, phosphoramides, phosphonium salts, phosphates, phenols, and a broad range of alkyl substrates including both secondary and primary alkyl iodides, bromides, and chlorides. Many of these electrophiles have been found to be incompatible with traditional palladium catalysed processes. 

Han F-S. Transition-metal-catalyzed Suzuki-Miyaura cross-coupling reactions a remarkable advance from palladium to nickel catalysts. Chem Soc Rev. 2013 42 5270-5298. 

---