The stereochemical divergent synthesis of indolyl-pyrrolidines was accomplished using an imidazoline-aminophenol (IAP)–Ni(OAc)₂ complex and a bis(imidazolidine)pyridine (PyBidine)–Cu(OTf)₂ complex. The former catalyzed exo′-selective asymmetric [3 + 2] cyclization of iminoesters with indolyl nitroalkenes, and the latter catalyzed the reaction in an endo-selective manner. These catalysts are tolerant toward highly functional substrates that supply chiral indolyl-pyrrolidine hybrids.