Solvent coordination to palladium can invert the selectivity of oxidative addition.

ABSTRACT: Reaction solvent was previously shown to influence the selectivity of Pd/P ^t Bu₃-catalyzed Suzuki-Miyaura cross-couplings of chloroaryl triflates. The role of solvents has been hypothesized to relate to their polarity, whereby polar solvents stabilize anionic transition states involving [Pd(P ^t Bu₃)(X)]^- (X = anionic ligand) and nonpolar solvents do not. However, here we report detailed studies that reveal a more complicated mechanistic picture. In particular, these results suggest that the selectivity change observed in certain solvents is primarily due to solvent coordination to palladium. Polar coordinating and polar noncoordinating solvents lead to dramatically different selectivity. In coordinating solvents, preferen

SUBMITTER: Elias EK 

PROVIDER: S-EPMC8827013 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature