Synthesis of Biaryls via a Nickel(0)-Catalyzed Cross-Coupling Reaction of Chloroarenes with Arylboronic Acids

Abstract

The cross-coupling reaction of arylboronic acid with chloroarenes to give biaryls was carried out in high yields at 70-80 degrees C in the presence of a nickel(0) catalyst and K(3)PO(4) (3 equiv) in dioxane or benzene. The nickel(0) catalyst in situ prepared from NiCl(2).L (L = dppf, 2PPh(3)) (3-10 mol %) and 4 equiv of BuLi at room temperature was recognized to be most effective. The reaction can be applicable to a wide range of chloroarenes having an electron-withdrawing or an electron-donating group such as 4-NC, 4-CHO, 2- or 4-CO(2)Me, 4-COMe, 4-NHAc, 4-Me, 4-OMe, 4-NH(2), and 4-NMe(2). The Hammett's plot of the substituent effect of chloroarenes revealed that the reaction involves a rate-determining oxidative addition of chloroarenes to the nickel(0) complex.

Estratégias para estudo das correlações de energia livre em acoplamento aril-aril de Suzuki: elucidando ciclos catalíticos através da equação de Hammett

“…Essa inclinação positiva repete o resultado encontrado quando foi avaliada a influência dos grupos substituintes em para nos ácidos arilborônicos quando acoplados com tosilatos via catalisador NiCl 2 (PCy 3 ) 2 . Miyaura 15 reportou a investigação dos parâmetros de Hammett na reação de Suzuki de ácidos arilborônicos com 3-metoxiclorobenzeno catalisada por NiCl 2 (dppf). Ao montar o gráfico, constatou-se que as razões entre as bifenilas obtidas foram praticamente as mesmas, ou seja, o gráfico gerou uma reta.…”

Syntheses of Dithienylcyclopentene Optical Molecular Switches

“…There is currently a great deal of interest in the coupling of aryl chlorides with arylboronic acids. [34] Although nickel catalysts are useful for this reaction as has been demonstrated by Indolese [35] and Saito et al, [36] most studies have focussed on palladium catalysts. Recently significant breakthroughs in this area have been made by Fu, [37] Buchwald, [38] Nolan, [39] Beller [40] and Trudell.…”

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.…”