Divergent Total Syntheses of (−)‐Daphnilongeranin B and (−)‐Daphenylline |
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| Authors: | Xinkan Yang Houqiang Lv Xiaoru Shao Cheng Tao Dr Huifei Wang Dr Bin Cheng Dr Yun Li Jingjing Guo Jing Zhang Prof?Dr Hongbin Zhai |
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| Institution: | 1. The State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, China;2. Shenzhen Engineering Laboratory of Nano Drug Slow Release, Key Laboratory of Chemical Genomics, Shenzhen Graduate School of Peking University, Shenzhen, China;3. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, China |
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| 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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| Keywords: | alkaloids asymmetric total synthesis [3+2] cycloaddition natural products rearrangement |
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