Computational Characterization of the Role of the Base in the Suzuki−Miyaura Cross-Coupling Reaction
Citations Over TimeTop 10% of 2005 papers
Abstract
The role of the base in the transmetalation step of the Suzuki-Miyaura cross-coupling reaction is analyzed computationally by means of DFT calculations with the Becke3LYP functional. The model system studied consists of Pd(CH=CH2)(PH3)2Br as the starting catalyst complex, CH2=CHB(OH)2 as the organoboronic acid, and OH- as the base. The two main mechanistic proposals, consisting of the base attacking first either the palladium complex or the organoboronic acid, are evaluated through geometry optimization of the corresponding intermediates and transition states. Supplementary calculations are carried out on the uncatalyzed reaction and on a process where the starting complex is Pd(CH=CH2)(PH3)2(OH). These calculations, considered together with available experimental data, strongly suggest that the main mechanism of transmetalation in the catalytic cycle starts with the reaction of the base and the organoboronic acid.
Related Papers
- → A novel palladium-catalyzed homocoupling reaction initiated by transmetallation of palladium enolates(2002)89 cited
- → Electrochemical Synthesis of a Tetradentate Copper N-Heterocyclic Carbene Calix[4]arene and Its Transmetalation to Palladium: Activity of the Palladium Complex in Suzuki–Miyaura Cross-Coupling(2013)46 cited
- → Direct Observation of Gold/Palladium Transmetalation in an Organogold Heck Reaction(2011)27 cited
- → Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions(2023)17 cited
- → Mechanism of Cu-catalyzed iododeboronation: A description of ligand-enabled transmetalation, disproportionation, and turnover in Cu-mediated oxidative coupling reactions(2023)1 cited