RESUMO
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.
RESUMO
AuClL(1)/PdCl2L(2)2 cocatalyzed coupling of Ar(1)X and Ar(2)SnBu3 is feasible for bulky Ar(1), provided that at least one ligand on Pd is not strongly coordinating. This can be achieved in situ by Au/Pd ligand exchange if L(1) is weakly coordinating. When the exchange is slow, independent preparation of appropriate catalysts is recommended.
