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Total Synthesis of (6 R ,10 R ,13 R ,14 R ,16 R ,17 R ,19 S ,20 R ,21 R ,24 S , 25 S ,28 S ,30 S ,32 R ,33 R ,34 R ,36 S ,37 S ,39 R )‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product
Author(s) -
Kenton Nathaniel T.,
AduAmpratwum Daniel,
Okumu Antony A.,
Zhang Zhigao,
Chen Yong,
Nguyen Son,
Xu Jianyan,
Ding Yue,
McCarron Pearse,
Kilcoyne Jane,
Rise Frode,
Wilkins Alistair L.,
Miles Christopher O.,
Forsyth Craig J.
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.201711006
Subject(s) - total synthesis , chemistry , alkyne , stereoselectivity , alcohol , stereochemistry , convergent synthesis , medicinal chemistry , organic chemistry , catalysis
A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21−C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically.