Musaev Djamaladdin G, Liebeskind Lanny S
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322.
Organometallics. 2009 Jul 22;28(16):4639-4642. doi: 10.1021/om900602b.
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.
钯催化、羧酸铜（I）介导的有机硫化合物与硼酸的脱硫偶联反应机理的计算研究表明，必需的羧酸铜（I）发挥着多种重要作用。羧酸铜（I）增强了转金属化和碳-碳还原消除步骤：它作为一个活性转金属化中心，并提供一个至关重要的羧酸配体。羧酸配体不仅作为硼酸的活化剂，而且它还在钯中心取代一个膦配体，生成一个具有催化活性的单膦钯中间体。
