Divergent ring-opening coupling between cyclopropanols and alkynes under cobalt catalysis

Cobalt-diphosphine catalysts promote ring-opening coupling reactions between cyclopropanols and unactivated internal alkynes, affording either -alkenyl ketones or multisubstituted cyclopentenol derivatives in good yields with good to excellent regioselectivities. The chemoselectivity between these -alkenylation and [3 + 2] annulation reactions, which likely share a cobalt homoenolate as a key catalytic intermediate, is exquisitely controlled by the reaction conditions, with the solvent being a major controlling factor. The reactions are proposed to involve ring opening of cobalt cyclopropoxide into homoenolate, migratory insertion of the alkyne into the Co-C bond, and protodemetalation or intramolecular carbonyl addition of the resulting alkenylcobalt species. The feasibility of these reaction steps was supported by DFT calculations.