Palladium-Catalyzed Asymmetric Tandem Carbonylation-Heck Reaction of Cyclopentenes to Access Chiral Bicyclo[3.2.1]octenes.

A palladium-catalyzed asymmetric tandem carbonylation-Heck reaction of cyclopentenes with carbon monoxide (CO) has been disclosed. This desymmetrization procedure afforded a series of bicyclo[3.2.1]octenes with one chiral quaternary and one tertiary carbon center in good yields with good enantioselectivities. This reaction proceeds via an acyl-palladium intermediate, followed by migratory insertion of the alkenes.