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Divergent Total Syntheses of (-)-Daphnilongeranin B and (-)-Daphenylline
Xiaoming Chen1, Hai-Jun Zhang1, Xinkan Yang2
1Shenzhen Engineering Laboratory of Nano Drug Slow Release, Key Laboratory of Chemical Genomics, Shenzhen Graduate School of Peking University, Shenzhen, 518055, China.
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.
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