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Interrupted Pummerer Reaction in Latent‐Active Glycosylation: Glycosyl Donors with a Recyclable and Regenerative Leaving Group
Author(s) -
Shu Penghua,
Xiao Xiong,
Zhao Yueqi,
Xu Yang,
Yao Wang,
Tao Jinyi,
Wang Hao,
Yao Guangmin,
Lu Zimin,
Zeng Jing,
Wan Qian
Publication year - 2015
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.201507861
Subject(s) - glycoside , glycosyl , glycosylation , chemistry , glycosyl donor , phenylethanoid , pummerer rearrangement , organic chemistry , combinatorial chemistry , stereochemistry , biochemistry , catalysis , acetic anhydride
Latent O‐glycosides, 2‐(2‐propylthiol)benzyl (PTB) glycosides, were converted into the corresponding active glycosyl donors, 2‐(2‐propylsulfinyl)benzyl (PSB) glycosides, by a simple and efficient oxidation. Treatment of the PSB donor and various acceptors with triflic anhydride provided the desired glycosides in good to excellent yields. The leaving group, which was activated by an interrupted Pummerer reaction, can be recycled (PSB‐OH) and regenerated as the precursor (PTB‐OH). A natural hepatoprotective glycoside, leonoside F, was efficiently synthesized in a convergent [3+1] manner with this newly developed method. The present total synthesis also led to a structural revision of this phenylethanoid glycoside.