Alkene hydroamination with a chiral zirconium catalyst. Connecting ligand design, precatalyst structure and reactivity trends

New tethered bis(amidate) ligands have been designed and synthesized to established structure/function reactivity trends in zirconium catalyzed enantioselective cyclohydroamination. Ligands with electron withdrawing substituents have enhanced reactivity trends, while ligands that promote the formation of flexible and dynamic coordination modes have modest control of enantioselectivities. Well-defined coordination geometries are preferred for enantioselective hydroamination.127