Direct Access to Benzolactams and Benzolactones via Nickel Catalyzed Carbonylation with CO2

A new nickel catalyzed cross‐electrophile coupling for accessing γ‐lactams (isoindolinones) as well as γ‐lactones (isobenzofuranones) via carbonylation with CO 2 is documented. The protocol exploits the synergistic role of redox‐active Ni(II) complexes and AlCl 3 as a CO 2 activator/oxygen scavenger, leading to the formation of a wide range of cyclic amides and esters (28 examples) in good to high yields (up to 87 %). A dedicated computational investigation revealed the multiple roles played by AlCl 3 . In particular, the simultaneous transient protection of the pendant amino group of the starting reagents and the formation of the electrophilically activated CO 2 ‐AlCl 3 adduct are shown to concur in paving the way for an energetically favorable mechanistic pathway.