Highly Enantioselective Construction of Hajos–Wiechert Ketone Skeletons via an Organocatalytic Vinylogous Michael/Stetter Relay Sequence

A highly enantioselective supramolecular iminium-catalyzed vinylogous Michael addition/Stetter relay sequence has been developed. This transformation provided a series of Hajos–Wiechert-type fused bicyclic diones with three continuous stereogenic centers in good yields with excellent enantioselectivities. The obtained products can be easily transformed into other structures with potential synthetic value.