1222196-03-3Relevant academic research and scientific papers
Role of dppf Monoxide in the Transmetalation Step of the Suzuki-Miyaura Coupling Reaction
Payard, Pierre-Adrien,Bohn, Antoine,Tocqueville, Damien,Jaouadi, Khaoula,Escoude, Emile,Ajig, Sanaa,Dethoor, Annie,Gontard, Geoffrey,Perego, Luca Alessandro,Vitale, Maxime,Ciofini, Ilaria,Wagschal, Simon,Grimaud, Laurence
, p. 1120 - 1128 (2021)
Diphosphine ligands are frequently used in palladium-catalyzed Suzuki-Miyaura (S-M) reactions. Despite their widespread application in both academic and industrial settings, their role in the B-to-Pd transmetalation has not been firmly established. We combined electrochemistry, NMR spectroscopy, and DFT calculations to elucidate the role of dppf (1,1′-bis(diphenylphosphino)ferrocene) in this key elementary step of the S-M reaction. We observed that excess dppf inhibits transmetalation involving PhB(OH)2 and dppf-ligated arylpalladium(II) complexes, while an optimal [base]/[PhB(OH)2] ratio maximizes the concentration of a [Pd-O-B] key intermediate. In situ oxidation of dppf to the diphosphine monoxide dppfO can take place in the presence of base, leading to dppfO-ligated arylpalladium(II) complexes, which readily undergo transmetalation at room temperature. These findings suggest guidelines for the rational optimization of diphosphine-promoted S-M reactions.
