Some new aspects of asymmetric catalysis with chiral ferrocenyl ligands

Chiral bindentate ferrocenyl ligands have been used in a variety of asymmet ric catalytic reactions. Three different recent developments are illustrate d here. Firstly, using P, N systems containing a p-acidic phosphine and a b ulky pyrazole very high enantioselectivities were obtained in the Pd-cataly zed hydrosilylation of norbornene with trichlorosilane (up to 99% ee). Seco ndly, selective functionalization of the "lower" Cp ring affords derivative s suited for dendrimer synthesis. Well characterized dendrimers containing up to eight peripheral Josiphos units were used in the Rh-catalyzed hydroge nation of dimethyl itaconate giving ee's up to 98.6%. Finally, the enantios elective Ir-catalyzed addition of aniline to norbornene (up to 95% eel, via N-H activation, was achieved using dinuclear Ir(I) complexes as catalyst p recursors.