Novel chiral PN,N-type ligands (4) derived from (R)-(S)-PPFNH2-R (6) and 2-pyridinecarboxaldehydes were employed in Ru(II)-catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate. Up to 99% yield with 95% e.e. for cis-isomer and 90% e.e. for trans-isomer was obtained on Ru(II)/4a. (C) 2003 Elsevier B.V. All rights reserved.