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Biogenesis‐Guided Synthesis and Structural Revision of Sarocladione Enabled by Ruthenium‐Catalyzed Endoperoxide Fragmentation
Author(s) -
Ning Yuhan,
Tian Hailong,
Gui Jinghan
Publication year - 2021
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.202101451
Subject(s) - ruthenium , biogenesis , chemistry , fragmentation (computing) , catalysis , diketone , combinatorial chemistry , cleavage (geology) , steroid , stereochemistry , organic chemistry , computer science , materials science , biochemistry , fracture (geology) , hormone , composite material , gene , operating system
Abstract Sarocladione is the first 5,10:8,9‐diseco‐steroid with a 14‐membered macrocyclic diketone framework to have been isolated from a natural source. Herein we report a biomimetic synthesis of sarocladione in only two or seven steps from inexpensive, commercially available ergosterol. The key feature of this synthesis was a novel ruthenium‐catalyzed endoperoxide fragmentation, which transformed various saturated endoperoxides into olefinic diketones by cleavage of two C−C bonds. This synthesis allowed us to unambiguously determine the structure of sarocladione and provided experimental support for its revised biosynthetic origin. This work also vividly demonstrates that consideration of the biogenesis is a powerful tool for elucidating the structures of natural products.