Two methods for the synthesis of new axially chiral bipyridine N,N'-dioxides based on catalytic [2+2+2] cyclotrimerization of diynes with nitriles were developed. The N,N'-dioxides were used as catalysts in enantioselective allylation of benzaldehyde with allyltrichlorosilane and aldol reaction of trichlorosilyl ketene acetal of methyl acetate with acetophenone.