Ligand- and Substrate-Controlled Chemodivergent Pd-Catalyzed Annulations of Cyclic β‑Keto Esters with 3‑Aryl‑2H‑azirines

Chemodivergent Pd-catalyzed annulations of cyclic β-keto esters with 3-aryl-2H-azirines have been developed to provide rapid access to eight-membered ring lactams, bicyclic 3,4-dihydro-2H-pyrrole derivatives, and (E)-methyl [2-(2-oxocyclohexylidene)-2-phenylethyl]­carbamates with high efficiency. The chemoselectivity can be determined by tuning the mono- or bisphosphine ligands as well as the substrate structure of cyclic β-keto esters.