A palladium-catalyzed carbonylative [5+1] cycloaddition of N-tosyl vinylaziridines with CO has been developed. This protocol affords an efficient and practical approach for solvent-controlled divergent synthesis of α,β-unsaturated δ-lactams in dimethylformamide and β,γ-unsaturated δ-lactams in tetrahydrofuran in good to excellent yields. Significantly, the step- and atom-economical reactions are more regioselective toward [5+1] cycloaddition than toward [3+1] cycloaddition.

Scheme 1. [Pd II ]CF 2 -Involved Transfer Reactions Letter pubs.acs.org/OrgLett