title: In Situ Generation of ArCu from CuF2 Makes Coupling of Bulky Aryl Silanes Feasible and Highly Efficient.
abstract: A bimetallic system of Pd/CuF2, catalytic in Pd and stoichiometric in Cu, is very efficient and selective for the coupling of fairly hindered aryl silanes with aryl, anisyl, phenylaldehyde, p-cyanophenyl, p-nitrophenyl, or pyridyl iodides of conventional size. The reaction involves the activation of the silane by Cu(II), followed by disproportionation and transmetalation from the Cu(I)(aryl) to Pd(II), upon which coupling takes place. Cu(III) formed during disproportionation is reduced to Cu(I)(aryl) by excess aryl silane, so that the CuF2 system is fully converted into Cu(I)(aryl) and used in the coupling. Moreover, no extra source of fluoride is needed. Interesting size selectivity towards coupling is found in competitive reactions of hindered aryl silanes. Easily accessible [PdCl2 (IDM)(AsPh3)] (IDM = 1,3-dimethylimidazol-2-ylidene) is by far the best catalyst, and the isolated products are essentially free from As or Pd (<1 ppm). The mechanistic aspects of the process have been experimentally examined and discussed.
authors.affiliation: IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011, Valladolid, Spain.
authors.forename: Juan
authors.initials: J
authors.lastname: delPozo
authors.affiliation: IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011, Valladolid, Spain. casares@qi.uva.es.
authors.forename: Juan A
authors.initials: JA
authors.lastname: Casares
authors.affiliation: IU CINQUIMA/Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011, Valladolid, Spain. espinet@qi.uva.es.
authors.forename: Pablo
authors.identifier: http://orcid.org/0000-0001-8649-239X
authors.initials: P
authors.lastname: Espinet
keywords: bimetallic catalysis; copper; cross-coupling; palladium; silanes