A wide range of NCN pincer palladium complexes, [4-tert-butyl-2,6-bis(N-alkylimino)phenyl]-chloropalladium (alkyl = n-butyl, benzyl, cyclohexyl, tert-butyl, adamantyl, phenyl, 4-methoxyphenyl), were readily prepared from trans-(4-tert-butyl-2,6-diformylphenyl)chlorobis(triphenylphosphine)pall adium via dehydrative introduction of the corresponding alkylimino ligand groups (ligand introduction route) in excellent yields (71 -98%). NMR studies on this route for forming pincer complexes revealed the intermediacy of [4-tert-butyl-2,6-bis(N-alkylimino)phenyl]chlorobis(triphenylphosphine)p aliadium which is in equilibrium with the corresponding NCN pincer complexes via coordination/dissociation of the intramolecular imino groups and triphenylphosphine ligands. A series of chiral NCN pincer complexes bearing pyrroloimidazoione units as the trans-chelating donor groups, [4-tert-butyl-2,6-bis{(3R,7aS)-2-phenyihexahydro-1H-pyrrolo[1,2-c]-imida zol-1 -on-3-yl}phenyl]chloropalladium, were also prepared from the same precursor via condensation with proline anilides in high yields. The catalytic properties of the NCN imino and the NCN pyrroloimidazolone pincer palladium complexes were examined in the Heck reaction and the asymmetric Michael reaction to demonstrate their high catalytic activity and high enantioselectivity.