Diverse Mechanistic Pathways and Selectivities in Organo-f-Element-Catalyzed Hydroamination. Intermolecular Organolanthanide-Catalyzed Alkyne and Alkene Hydroamination

Lanthanide metallocenes catalyze the regiospecific intermolecular addition of primary amines to acetylenic, olefinic, and diene substrates at rates which are ∼1/1000 those of the most rapid intramolecular analogues. Kinetic and mechanistic data argue for turnover-limiting C⋮C/CC insertion into a Ln−N bond, followed by protonolysis of the resulting Ln−C bond.