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

Chemodivergent Pd-catalyzed annulations of cyclic ß-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 ß-keto esters.

Cascade Reaction of 2-Naphthols and Azirines: One-Pot Synthesis of C-3 Naphthol-Substituted Benzo[e]indoles.

A copper-catalyzed annulation of 3-aryl-2H-azirines with 2-naphthols has been developed for the rapid assembly of C-3-naphthol-substituted benzo[e]indoles in one pot. This cascade reaction was realized through dearomatic nucleophilic ring opening of azirine, intramolecular cyclization, and oxidative cross-dehydrogenative coupling to furnish the important unreported π-expanded naphthol/benzo[e]indole biaryls.