(-)-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.

À)-Daphnilongeranin Ba nd (À)-daphenylline are two hexacyclic Daphniphyllum alkaloids,e ach containing ac omplex cagelike backbone.D escribed herein are the first asymmetric total synthesis of (À)-daphnilongeranin Ba nd ab ioinspired synthesis of (À)-daphenylline with an unusual Ering embedded in ac agelike framework. The key features include an intermolecular [3+ +2] cycloaddition, al ate-stage aldol cyclization to install the Fring of daphnilongeranin B, and ab ioinspired cationic rearrangement leading to the tetrasubstituted benzene ring of daphenylline. Angewandte Chemie Communications 949Angew.C hem. Int.E d. 2018, 57,9 47 -951