889649-63-2Relevant academic research and scientific papers
Mechanism of the palladium-catalyzed homocoupling of arylboronic acids: Key involvement of a palladium peroxo complex
Adamo, Carlo,Amatore, Christian,Ciofini, Ilaria,Jutand, Anny,Lakmini, Hakim
, p. 6829 - 6836 (2007/10/03)
The mechanism of the palladium-catalyzed homocoupling of arylboronic acids Arb(OH)2 (Ar = 4-z-C6H4 with Z = MeO, H, CN) in the presence of dioxygen, leading to symmetrical biaryls, has been fully elucidated. The peroxo complex (η2-O2)PdL2 (L = PPh3), generated in the reaction of dioxygen with the Pd(0) catalyst, was found to play a crucial role. Indeed, it reacts with the arylboronic acid to generatye an adduct (coordination of one oxygen atom of the peroxo complex to the oxophilic boron atom of the arylboronic acid) characterized by 21P NMR spectroscopy and ab initio calculations. This adducts reacts with a second molecule of arylboronic acid to generate trans-ArPd(OH)L2 complexes. A transmetalation by the arylboronic acid gives trans-ArPdArL2 complexes. The biaryl is then released in a reductive elimination. This reaction is at the origin of the formation of biaryls as byproducts in palladium-catalyzed Suzuki-Miyaura reactions when they are not conducted under oxygen-free atmosphere.
