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Divergent Total Syntheses of (−)‐Daphnilongeranin B and (−)‐Daphenylline
Author(s) -
Chen Xiaoming,
Zhang HaiJun,
Yang Xinkan,
Lv Houqiang,
Shao Xiaoru,
Tao Cheng,
Wang Huifei,
Cheng Bin,
Li Yun,
Guo Jingjing,
Zhang Jing,
Zhai Hongbin
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201709762
Subject(s) - ring (chemistry) , chemistry , cycloaddition , stereochemistry , aldol reaction , cationic polymerization , total synthesis , intermolecular force , benzene , molecule , organic chemistry , catalysis
(−)‐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.