The bread and butter of drug discovery in the pharmaceutical industry is the synthesis of complex scaffolds, including chiral heterocyclic motifs. However, general access remains a long-standing goal and challenge. Despite the high demand, the synthesis of some entities is limited by step-intensive and costly routes. To address these challenges, we herein present the development of a highly selective ruthenium-NHC catalyst that enables direct access to a broad range of chiral 6,5-heterocycles from readily available arenes.