Catalytic Intramolecular Ketone Alkylation with Olefins by Dual Activation

Two complementary methods for catalytic intramolecular ketone alkylation reactions with unactivated olefins, resulting in Conia‐ene‐type reactions, are reported. The transformations are enabled by dual activation of both the ketone and the olefin and are atom‐economical as stoichiometric oxidants or reductants are not required. Assisted by Kool’s aniline catalyst, the reaction conditions can be both pH‐ and redox‐neutral. A broad range of functional groups are thus tolerated. Whereas the rhodium catalysts are effective for the formation of five‐membered rings, a ruthenium‐based system that affords the six‐membered ring products was also developed. The cooperative activation of a ketone and an olefin by 2‐aminopyridine and a rhodium or ruthenium catalyst leads to Conia‐ene‐type products with excellent regioselectivity. These transformations can be conducted under nearly pH‐ and redox‐neutral conditions, and are thus applicable to both alkyl and aryl olefins with a broad range of functional groups.