Asymmetric cross-coupling of achiral biaryl ditriflates with aryl Grignard reagents in the presence of 1 equiv of lithium bromide and 5 mol % of palladium complex PdCl2[(S)-alaphos], where alaphos stands for (2-dimethylamino)propyldiphenylphosphine, gave axially chiral monophenylation products with high enantioposition-selectivity. The remaining triflate group in the monophenylation products was substituted with carboxyl and diphenylphosphino groups through palladium-catalyzed carbonylation and diphenylphosphinylation, respectively. (C) 1999 Elsevier Science Ltd. All rights reserved.