Investigations into an anionic oxy-cope/transannular conjugate addition approach to 7,20-diisocyanoadociane.

An anionic oxy-Cope/transannular conjugate addition approach to the potent antimalarial 7,20-diisocyanoadociane is presented. The unexpected formation of undesired diastereomers in the key reaction led to the structural reassignment of previous products of this type of cascade and a reevaluation of the reversibility of the transannular ring closure. During efforts to coax the reaction toward the desired product, a transannular ene reaction provided tricyclic compounds relevant to the kempane diterpenoids.