The development of enantiomerically resolved, axially-chiral seven-membered N-heterocyclic carbene ( 7NHC) ligands for palladium is described. These 7NHC ligands are derived from enatiomerically pure 2,2′-diamino-6,6′-dimethylbiphenyl, which is transformed via a synthetic sequence consisting of ortho-arylation, N-alkylation, and cyclization to afford seven-membered-ring amidinium salts. Synthesis of the seven-membered amidinium salts benefits from microwave irradiation, and in-situ metalation of the amidinium salts yields 7NHC–Pd II complexes. The chiral 7NHC–Pd complexes were examined as chiral catalysts under aerobic conditions in two intramolecular oxidative amination reactions of alkenes. In one case, enantioselectivities up to 63% ee were obtained, while the other substrate underwent cyclization to afford essentially racemic products. The catalytic data compare favorably to results obtained with a Pd II catalyst bearing a chiral five-membered-ring NHC ligand and, thereby, highlight the potential significance of this new class of chiral NHC ligands.