(R,S)-BINAPHOS-NI(0) AND (R,S)-BINAPHOS-PD(0) COMPLEXES - CHARACTERIZATION AND USE FOR ASYMMETRIC HYDROCYANATION OF NORBORNENE

Zerovalent nickel and palladium complexes bearing phosphine-phosphite ligand, (R,S)-BINAPHOS, have been prepared. The complexes M(binaphos)( 2) (M=Ni, Pd) were characterized on the basis of P-31 NMR spectroscopy and FAB mass spectroscopy. These complexes have been applied to asymm etric hydrocyanation of norbornene, giving the corresponding exo-nitri le, Enantioselectivities up to 48% ee have been obtained with the pall adium complex as catalyst. This is the highest ee ever reported using norbornene as a substrate, Nickel catalyst was more active but less en antioselective (up to 40% ee). The palladium-catalyzed reaction was gr eatly inhibited by adding excess ligand. (C) 1997 Published by Elsevie r Science Ltd.