A new class of chiral ruthenium catalysts is introduced in which ruthenium is cyclometalated by two 7-methyl-1,7-phenanthrolinium heterocycles, resulting in chelating pyridylidene remote N-heterocyclic carbene ligands (rNHCs). The overall chirality results from a stereogenic metal center featuring either a Lambda or Delta absolute configuration. This work features the importance of the relative metal-centered stereochemistry. Only the non-C-2-symmetric chiral-at-ruthenium complexes display unprecedented catalytic activity for the intramolecular C(sp(3))-H amidation of 1,4,2-dioxazol-5-ones to provide chiral gamma-lactams with up to 99:1 er and catalyst loadings down to 0.005 mol % (up to 11 200 TON), while the C-2-symmetric diastereomer favors an undesired Curtius-type rearrangement. DFT calculations elucidate the origins of the superior C-H amidation reactivity displayed by the non-C-2-symmetric catalysts compared to related C-2-symmetric counterparts.