Enantioselective Pd-catalysed allylation with BINOL-derived monodentate phosphite and phosphoramidite ligands

P-monodentate phosphite (1) and phosphoramidite (2) ligands have been synthesised from (S)-BINOL. The phosphoramidite 2 showed higher enantioselectivity than its phosphite analogue 1 and provided good enantioselectivity 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).