Ligand-Controlled Regiodivergent Asymmetric [5 + 2] and [3 + 2] Annulations of Vinyl Indoloxazolidones Catalyzed by Palladium.

Here, we present palladium-catalyzed regiodivergent asymmetric annulations of vinyl indoloxazolidones, which can act as 1,5-carbodipoles or 1,3-carbodipoles by tuning the chiral ligands and conditions, in the assemblies with sulfamate-derived cyclic imines and even activated alkenes. A diversity of polycyclic products are generally constructed with high regio- and enantioselectivity.