title: On the Mechanism of Pd(0)-Catalyzed, Cu(I) Carboxylate-Mediated Thioorganic-Boronic Acid Desulfitative Coupling. A Non-innocent Role for Carboxylate Ligand.
abstract: Computational studies of the mechanism of the Pd-catalyzed, Cu(I)-carboxylate-mediated desulfitative coupling of thioorganics with boronic acids have determined that the requisite Cu(I)-carboxylate plays multiple important roles. The Cu(I)-carboxylate enhances both the transmetalation and the C-C reductive elimination steps: it acts as a reactive transmetalation center and it provides a vital carboxylate ligand. The carboxylate ligand functions not only as an activator for the boronic acid, but it also displaces a phosphine ligand at the palladium center generating a catalytically competent mono-phosphine-palladium intermediate.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322.
authors.forename: Djamaladdin G
authors.initials: DG
authors.lastname: Musaev
authors.forename: Lanny S
authors.initials: LS
authors.lastname: Liebeskind