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Scalable Total Synthesis of rac ‐Jungermannenones B and C
Author(s) -
Liu Weilong,
Li Houhua,
Cai PeiJun,
Wang Zhen,
Yu ZhiXiang,
Lei Xiaoguang
Publication year - 2016
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.201511659
Subject(s) - regioselectivity , allylic rearrangement , isomerization , radical cyclization , chemistry , geraniol , scalability , combinatorial chemistry , stereochemistry , medicinal chemistry , computer science , catalysis , organic chemistry , chromatography , database , essential oil
Reported is the first scalable synthesis of rac ‐jungermannenones B and C starting from the commercially available and inexpensive geraniol in 10 and 9 steps, respectively. The unique jungermannenone framework is rapidly assembled by an unprecedented regioselective 1,6‐dienyne reductive cyclization reaction which proceeds through a vinyl radical cyclization/allylic radical isomerization mechanism. DFT calculations explain the high regioselectivity observed in the 1,6‐dienyne reductive radical cyclization.