Unconventional Ligand‐to‐Catalyst Ratio for the Distal C−C Bond Formation via C−H Activation and Chain‐Walking

A mechanism‐navigated enantioselective alkylation of an indole C2 C−H bond with an internal alkene was developed. Under the unconventional ligand‐to‐metal catalyst ratio, a moderate enantiomeric ratio (er), ranging from 70:30 to 88:12, was achieved with our original ligand. We propose that chain‐walking and bond formation are mechanistically independent and suggest that hydridoiridium generated from the C−H source does not play a role in the chain‐walking process.