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Bioinspired Asymmetric Synthesis of Hispidanin A
Author(s) -
Li Fuzhuo,
Tu Qian,
Chen Sijia,
Zhu Lei,
Lan Yu,
Gong Jianxian,
Yang Zhen
Publication year - 2017
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.201700838
Subject(s) - natural product , yield (engineering) , chemistry , stereochemistry , rhizome , terpenoid , combinatorial chemistry , materials science , biology , botany , metallurgy
The first enantiospecific synthesis of hispidanin A ( 4 ), a dimeric diterpenoid from the rhizomes of Isodon hispida, was achieved with a longest linear sequence of 12 steps in 6.5 % overall yield. A key component is the use of the abundant and naturally occurring diterpenoids (+)‐sclareolide and (+)‐sclareol as starting materials, which enables the gram‐scale preparation of the key intermediates totarane ( 1 ) and s‐ trans ‐12E,14‐labdadien‐20,8β‐olide ( 2 ). Subsequently a thermal or an erbium‐catalyzed intermolecular Diels–Alder reaction of totarane ( 1 ) with labdadienolide ( 2 ) provide convergent and rapid access to the natural product hispidanin A ( 4 ). The synthetic studies have offered significant impetus for the efficient construction of these architecturally complex natural products.