Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product
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 ox...
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| Veröffentlicht in: | Angewandte Chemie International Edition 2018-01, Vol.57 (3), p.805-809 |
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| creator | Kenton, Nathaniel T. Adu‐Ampratwum, 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. |
| description | 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.
A convergent and stereospecific total synthesis of the previously assigned structure of the marine neurotoxin azaspiracid‐3 reveals non‐identity with the natural product. Therefore structural revision of the primary azaspiracids is necessary. |
| doi_str_mv | 10.1002/anie.201711006 |
| format | Article |
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A convergent and stereospecific total synthesis of the previously assigned structure of the marine neurotoxin azaspiracid‐3 reveals non‐identity with the natural product. 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| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2018-01, Vol.57 (3), p.805-809 |
| issn | 1433-7851 1521-3773 |
| language | eng |
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| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Alcohols Alkynes azaspiracids Carboxylic acids Mass spectrometry Mass spectroscopy natural products Oxidation structure elucidation Synthesis Tartaric acid total synthesis toxins |
| title | Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product |
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