Divergent Total Syntheses of (−)‐Daphnilongeranin B and (−)‐Daphenylline

This is the authors' abstract. We don't add key points for this paper.

Abstract (−)‐Daphnilongeranin B and (−)‐daphenylline are two hexacyclic Daphniphyllum alkaloids, each containing a complex cagelike backbone. Described herein are the first asymmetric total synthesis of (−)‐daphnilongeranin B and a bioinspired synthesis of (−)‐daphenylline with an unusual E ring embedded in a cagelike framework. The key features include an intermolecular [3+2] cycloaddition, a late‐stage aldol cyclization to install the F ring of daphnilongeranin B, and a bioinspired cationic rearrangement leading to the tetrasubstituted benzene ring of daphenylline.