Well‐Defined Anilido–Imine Iron(II) Complexes for Catalytic Intramolecular Alkene Hydroamination of Primary Amines

Despite the appeal of the scientific community for alkene hydroamination methodology to straightforwardly access valuable N ‐containing compounds from ubiquitous amines and alkenes, there is still a need to develop sustainable catalysts for the direct addition of simple and free amines with high atom efficiency. We herein report the synthesis and characterization of an array of structurally defined three‐coordinate anilido–imine Fe(II) alkyl complexes that show high catalytic activity and selectivity in the intramolecular hydroamination of unprotected primary amines tethered to unactivated alkenes. The influences of steric and electronic ligand variations on the catalytic efficiency of the process were examined. They led to the development of an anilido–imine Fe(II) catalyst far more active than previously reported β ‐diketiminate Fe(II) catalysts, exhibiting even catalytic activity at room temperature and displaying broader scope.