Diastereomeric pure thienylpyridines were prepared and assessed in the enantioselective palladium-catalyzed allylic substitution of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate and copper-catalyzed cyclopropanation of styrene with ethyl diazoacetate. These ligands provided unreactive palladium catalysts but effective copper catalysts affording however low enantioexcesses. (C) 2002 Elsevier Science B.V. All rights reserved.