Allylation of 1,5-dimethylbarbituric acid (BS) with allyl ace-yl)phosphane with optically active primary amines. An optimisation of this ligand type showed that the substituents at tate using in situ catalysts of palladium(II) acetylacetonate and chiral phosphane imine ligands results in the enantiose-the stereogenic center in the imine part should be a hydroxymethyl group and a bulky alkyl group, with the best ligand lective formation of 5-allyl-1,5-dimethylbarbituric acid (ABS) as the main product with up to 34% ee and 3,5-diallyl-1,5-being the L-tert-leucinol derivative. A screening of other types of chiral ligand, e.g. phosphane amines and phosphane dimethylbarbituric acid (AABS) as a possible by-product, also with up to 34% ee. This reaction is a type of allylic alky-trisimines, has also been performed. NMR experiments and a molecular modelling study of the cation [(η 3 -allyl)Pd(2a) 2 ] + lation, the stereoselectivity of which is difficult to control because the new stereocenter is formed in the nucleophile at-were carried out (tripos force field). The enantioselectivity of the phosphane imine ligands is explained by an interaction tacking from the side opposite to the metal atom. Classical optically active ligands do not give any enantioselectivity in of the chiral side arm of one of the ligands, which extends to about 3 A ˚above the allyl plane, with the incoming nucleo-this palladium-catalysed reaction. Chiral phosphane imine ligands, however, are a successful class of compound, synthe-phile. sized by Schiff base condensation of 2-formylphenyl(diphen-