A series of substrates containing a vinylic bromide were employed in a copper-free methodology using bidendate NHC ligands. The desired compounds are generally obtained with good enantioselectivity and good regioselectivity. Importantly the copper-catalyzed system afforded a lower enantioselectivity value. The catalytic products could be transformed into a broad scope of new 1,1-disubstituted olefins in a single step transformation without erosion of the enantioselectivity.