Palladium acetate [Pd(OAc)(2)]-catalyzed Hiyama cross-coupling of arenediazonium salts with organosilanes was found to generate biaryl products in high yields in alcoholic solutions. The simple and efficient protocol does not require any bases, ligands, or air/moisture. The transformation can tolerate either electron-donating or electron-withdrawing functional groups. Theoretical studies show that the transmetalation is the rate-limiting step for the cross-coupling reaction and both acetate and tetrafluoroborate anions may be involved in the direct reaction with the silicon atom.

A novel difunctionalization reaction of vinylarenes with cyclic ethers has been developed by copper catalysis via direct activation of alpha-sp(3) C-H bonds of oxygen in the presence of 1-1.2 equiv of TBHP under mild aerobic conditions. The reaction shows excellent regioselectivities and good functional group tolerance to give the oxyalkylated products of vinylarenes.

Palladium-catalyzed Hiyama-type cross-coupling reactions of various arenesulfinates with organosilanes were achieved in good to excellent yields under aerobic conditions at 70 °C. Fluoride is essential, and tetrabutylammonium fluoride (TBAF) was shown to be the most efficient additive for these cross-coupling reactions. These cross-coupling reactions of the arenesulfinates provide high yields and show wide functional group tolerance, making them attractive alternative transformations to traditional cross-coupling approaches for carbon-carbon bond construction.