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Meroterpenoid Synthesis via Sequential Polyketide Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic Total Syntheses of Austalide Natural Products
[Image: see text] The first total synthesis of five austalide natural products, (±)-17S-dihydroaustalide K, (±)-austalide K, (±)-13-deacetoxyaustalide I, (±)-austalide P, and (±)-13-deoxyaustalide Q acid, was accomplished via a series of biomimetic transformations. Key steps involved polyketide arom...
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7007238/ https://www.ncbi.nlm.nih.gov/pubmed/30938997 http://dx.doi.org/10.1021/acs.joc.9b00142 |
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author | Ma, Tsz-Kan Parsons, Philip J. Barrett, Anthony G. M. |
author_facet | Ma, Tsz-Kan Parsons, Philip J. Barrett, Anthony G. M. |
author_sort | Ma, Tsz-Kan |
collection | PubMed |
description | [Image: see text] The first total synthesis of five austalide natural products, (±)-17S-dihydroaustalide K, (±)-austalide K, (±)-13-deacetoxyaustalide I, (±)-austalide P, and (±)-13-deoxyaustalide Q acid, was accomplished via a series of biomimetic transformations. Key steps involved polyketide aromatization of a trans,trans-farnesol-derived β,δ-diketodioxinone into the corresponding β-resorcylate, followed by titanium(III)-mediated reductive radical cyclization of an epoxide to furnish the drimene core. Subsequent phenylselenonium ion induced diastereoselective cyclization of the drimene completed the essential carbon framework of the austalides to access (±)-17S-dihydroaustalide K, (±)-austalide K, and (±)-13-deacetoxyaustalide I via sequential oxidations. Furthermore, (±)-13-deacetoxyaustalide I could serve as a common intermediate to be derivatized into other related natural products, (±)-austalide P and (±)-13-deoxyaustalide Q acid, by functionalizing the cyclic lactone moiety. |
format | Online Article Text |
id | pubmed-7007238 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-70072382020-02-10 Meroterpenoid Synthesis via Sequential Polyketide Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic Total Syntheses of Austalide Natural Products Ma, Tsz-Kan Parsons, Philip J. Barrett, Anthony G. M. J Org Chem [Image: see text] The first total synthesis of five austalide natural products, (±)-17S-dihydroaustalide K, (±)-austalide K, (±)-13-deacetoxyaustalide I, (±)-austalide P, and (±)-13-deoxyaustalide Q acid, was accomplished via a series of biomimetic transformations. Key steps involved polyketide aromatization of a trans,trans-farnesol-derived β,δ-diketodioxinone into the corresponding β-resorcylate, followed by titanium(III)-mediated reductive radical cyclization of an epoxide to furnish the drimene core. Subsequent phenylselenonium ion induced diastereoselective cyclization of the drimene completed the essential carbon framework of the austalides to access (±)-17S-dihydroaustalide K, (±)-austalide K, and (±)-13-deacetoxyaustalide I via sequential oxidations. Furthermore, (±)-13-deacetoxyaustalide I could serve as a common intermediate to be derivatized into other related natural products, (±)-austalide P and (±)-13-deoxyaustalide Q acid, by functionalizing the cyclic lactone moiety. American Chemical Society 2019-04-02 2019-05-03 /pmc/articles/PMC7007238/ /pubmed/30938997 http://dx.doi.org/10.1021/acs.joc.9b00142 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Ma, Tsz-Kan Parsons, Philip J. Barrett, Anthony G. M. Meroterpenoid Synthesis via Sequential Polyketide Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic Total Syntheses of Austalide Natural Products |
title | Meroterpenoid Synthesis
via Sequential Polyketide
Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic
Total Syntheses of Austalide Natural Products |
title_full | Meroterpenoid Synthesis
via Sequential Polyketide
Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic
Total Syntheses of Austalide Natural Products |
title_fullStr | Meroterpenoid Synthesis
via Sequential Polyketide
Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic
Total Syntheses of Austalide Natural Products |
title_full_unstemmed | Meroterpenoid Synthesis
via Sequential Polyketide
Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic
Total Syntheses of Austalide Natural Products |
title_short | Meroterpenoid Synthesis
via Sequential Polyketide
Aromatization and Radical Anion Cascade Triene Cyclization: Biomimetic
Total Syntheses of Austalide Natural Products |
title_sort | meroterpenoid synthesis
via sequential polyketide
aromatization and radical anion cascade triene cyclization: biomimetic
total syntheses of austalide natural products |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7007238/ https://www.ncbi.nlm.nih.gov/pubmed/30938997 http://dx.doi.org/10.1021/acs.joc.9b00142 |
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