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