Recent studies in asymmetric catalysis using ferrocenyl ligands

Chiral bidentate ferrocenyl ligands have been fined-tuned in terms of their steric and electronic properties, and thus adapted to a variety of reactio ns catalyzed by transition metals. The position of the two ligating units ( two different PR2 groups, two pyrazolyl, or a combination thereof) attached to the ferrocenylethyl fragment may be interchanged. A comparison of P,N-l igands with their corresponding inversed (N,P) counterpart is presented for the Pd-catalyzed allylic amination. Dendrimers containing Josiphos-type li gands up to the third generation have been prepared and used in e.g. Rh-cat alyzed hydrogenation reactions. The intramolecular Ir-catalyzed hydroaminat ion reaction has been found to require an acidic N-H functionality and the presence of co-catalytic amounts of base. Olefin isomerization was found to be an important competing side-reaction. Kinetic/mechanistic studies of th e Pd-catalyzed hydrosilylation of styrenes have been carried out.