A concise and highly stereoselective total synthesis of the Daphniphyllum alkaloids (−)‐daphenylline has been accomplished. The synthesis was started from (S)‐carvone and proceeded via a stereoselective Mg(ClO4)2‐catalyzed intramolecular amide addition cyclization, an intramolecular Diels–Alder reaction to construct the ABCD tetracyclic core architecture, and a Robinson annulation coupled with an oxidative aromatization sequence. Finally, the DF ring system was installed through an intramolecular Friedel–Crafts cyclization. The total synthesis of (−)‐daphenylline is achieved in 19 steps in the longest reaction sequence and in 7.6 % overall yield.

A concise total synthesis of (±)-minfiensine using all conventional methods and starting from commercial materials has been completed. The synthesis features a Fischer indole synthesis, a Heck alkylation of an intermediate ketone enolate, conversion of a ketone carbonyl into an epoxide, and transformation of the latter into an allylic alcohol.