A General Strategy for the Construction of Calyciphylline A-Type Alkaloids: Divergent Total Syntheses of (-)-Daphenylline and (-)-Himalensine A.

An efficient general strategy for the synthesis of the Daphniphyllum alkaloids via the rapid construction of a common core intermediate has been established, based on which a divergent total synthesis of (-)-daphenylline and (-)-himalensine A has been accomplished in 16 and 19 steps, respectively. The present work features an enantioselective Mg(ClO4 )2 -catalyzed intramolecular amidocyclization to construct the aza-bridged core structure; a Cu-catalyzed intramolecular cyclopropanation and subsequent phosphine-catalyzed Cope-type rearrangement to furnish the himalensine A scaffold; and a one-pot Diels-Alder/aromatization method to assemble the aromatic skeleton of daphenylline.