P-monodentate phosphite (1) and phosphoramidite (2) ligands have been synthesised from (S)-BINOL. Complexation of the new ligands with [Rh(CO)(2)Cl](2) and [Pd(allyl)Cl](2) has been found to give neutral and cationic complexes [Rh(CO)Cl(L)](2) and [Pd(allyl)(L)(2)]+BF4-, correspondingly. Applicability of these ligands in asymmetric C*-C, C*-N, C*-S bond formation and alkene hydrogenation reactions has been demonstrated. The phosphoramidite 2 showed higher enantioselectivity than its phosphite analogue I and provided good enantio selectivity in the Pd-catalysed allylic substitution of 1,3-diphenylallyl acetate with dimethyl malonate (up to 90% ee), sodium para-toluene sulfinate (up to 75% ee), pyrrolidine (up to 65% ee) and sodium diformylamide (up to 68% ee), as well as in the Rh-catalysed hydrogenation of dimethyl itaconate (up to 76% ee). (c) 2005 Elsevier B.V. All rights reserved.