First, a range of challenging styrene derivatives 1b-g with a halogen atom (e.g., F, Cl, Br), cyano, ester, or a phenyl group at the paraposition of the aromatic ring were examined, which gave the desired products 5a-f with high yields (45-83%) and good enantioselectivities (83-90% ee). Moreover, the reactions of vinylarenes substituted by OMe or Cl at the meta-position of the phenyl ring furnished products 5g and 5h with good results (84-89% ee). (Hetero)arenes that having S-, O-, and N-heteroaromatic ring also underwent the arylative cross-coupling smoothly, with the corresponding products 5i-m being obtained in 53-80% yields with 81-90% ee. Remarkably, this protocol can be successfully extended to 2-vinylnaphthalene derivatives, in which the reaction efficiency and enantioselectivity are relatively independent of the stereoelectronic nature of the aromatic ring. For instance, an array of 2vinylnaphthalene derivatives bearing bromo, ester, ketone, including Ac and Boc-protected hydroxyl groups at the 6-position undergo the cross-coupling reaction to furnish products 5n-r in satisfactory yields with high enantioselectivities (90-93% ee). Markedly, a range of other easily prepared polyaromatic substrates with extended aromatic systems, such as 2-vinyl-, and 3-vinyl-subsituted phenanthrenes, were also compatible with the three-component cross-coupling, as exemplified with the preparation of 5s and 5t in good yield with 92% and 90% ee, respectively. The absolute configuration of products 5n and 5o were determined by chiroptical methods and X-ray crystallographic analysis, respectively (see Supporting Information, section 7). Other chiral 1,1-diarylalkane products were assigned by analogy. Unfortunately, our effort to expand the catalytic system to sterically more hindered 1,1-and 1,2disubstited styrene derivatives met failure, with only two-component cross-coupling byproducts being observed (see Supporting Information, section 5).