A Ni(0)-catalyzed intramolecular carbonylative cycloaddition between 1,5-yne-imines and carbon monoxide (CO) is disclosed. When Ni(CO)3PCy3 was employed as a pre-catalyst, a variety of polycyclic α,β-unsaturated γ-lactams were prepared in up to 78% yield with 100% atom efficiency. Aza-nickelacycles, generated by the oxidative cyclization of yne-imines on the Ni(0) center, were experimentally confirmed as key intermediates. Moreover, diastereoselective transformations of the obtained products to afford highly substituted polycyclic γ-lactams with three contiguous carbon stereocenters are reported.
Key words
nickel-catalysis - carbonylative cycloaddition - α,β-unsaturated γ-lactams - aza-nickelacycle - yne-imines