title: Uncovering the mechanism of the Ag(I)/persulfate-catalyzed cross-coupling reaction of arylboronic acids and heteroarenes.
abstract: The catalytic cross-coupling of arylboronic acids with pyridines through single-electron oxidation provides efficient access to substituted heterocycles. Despite the importance of this reaction, very little is known about its mechanism, and as a consequence, it is unclear whether the full scope of the transformation has been realized. Here we present kinetic and spectroscopic evidence showing a high degree of complexity in the reaction system. The mechanism derived from these studies shows the activation of Ag(I) for reduction of persulfate and an off-cycle protodeboronation by the pyridine substrate. These results provide key mechanistic insights that enable control of the off-cycle process, thus providing higher efficiency and yield.
authors.affiliation: Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA.
authors.forename: Niki R
authors.initials: NR
authors.lastname: Patel
authors.forename: Robert A
authors.initials: RA
authors.lastname: Flowers
mesh_terms: D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D010084:Oxidation-Reduction; D011725:Pyridines / Q000737:chemistry*; D012834:Silver / Q000737:chemistry*; D013431:Sulfates / Q000737:chemistry*
chemical_list: D001897:Boronic Acids; D011725:Pyridines; D013431:Sulfates; D012834:Silver