A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels–Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee.
