A novel intramolecular cyclisation reaction of 1,3,2-oxazaphospholidines has been employed for the diastereoselective synthesis of chiral, non-racemic dihydrobenzazaphosphole ligands. The new ligands have been employed in enantioselective palladium-catalysed allylic substitution reactions. Scheme 3 Reagents and conditions: i) nBuLi, TMEDA, PhPCl 2 , BH 3 ؒSMe 2 Scheme 4 Reagents and conditions: i) nBuLi, TMEDA, PhP(O)Cl 2 , ii) Et 3 N, HSiCl 3 , BH 3 ؒSMe 2 . 1 PERKIN 2588