A mechanism‐navigated enantioselective alkylation of an indole C2 C–H bond with an internal alkene was developed. Under the inharmonious ligand‐to‐metal catalyst ratio, a moderate enantiomeric ratio (er) was achieved with our original ligand. We propose that chain‐walking and bond formation are mechanistically independent, and suggest that hydridoiridium does not play a role in the chain‐walking process.