The development of enantiomerically-resolved, axially-chiral seven-membered N-heterocyclic carbene ((7)NHC) ligands for palladium is described. These (7)NHC 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 7-membered amidinium salts benefits from microwave irradiation, and in-situ metalation of the amidinium salts yields (7)NHC-Pd(II) complexes. The chiral (7)NHC-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% e.e. 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.