a b s t r a c t Herein we provide an overview on the unique properties of the sterically demanding IBiox-[(À)-menthyl] • HOTf ligand (such as flexibility and sterics) and an application of this ligand in Pd-catalyzed asymmetric intra-and intermolecular a-arylation reactions. Furthermore we demonstrate the synthesis of novel NHCemetal complexes and a new bifunctional NHC ligand whilst insight into the mechanistic mode of action of IBiox-[(À)-menthyl] • HOTf in catalysis is provided.