Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?

We have shown for the first time that taxadiene (3) can be epoxidised in a regio- and diastereoselective manner to provide taxadiene-4(5)-epoxide (12) as a single diastereoisomer, and that this epoxide can be rearranged to give taxa-4(20),11(12)-dien-5α-ol (4). Furthermore, the epoxide 12 rearranges...

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Autores principales: Barton, Naomi A., Marsh, Benjamin J., Lewis, William, Narraidoo, Nathalie, Seymour, Graham B., Fray, Rupert, Hayes, Christopher J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6005263/
https://www.ncbi.nlm.nih.gov/pubmed/29997802
http://dx.doi.org/10.1039/c5sc03463a
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author Barton, Naomi A.
Marsh, Benjamin J.
Lewis, William
Narraidoo, Nathalie
Seymour, Graham B.
Fray, Rupert
Hayes, Christopher J.
author_facet Barton, Naomi A.
Marsh, Benjamin J.
Lewis, William
Narraidoo, Nathalie
Seymour, Graham B.
Fray, Rupert
Hayes, Christopher J.
author_sort Barton, Naomi A.
collection PubMed
description We have shown for the first time that taxadiene (3) can be epoxidised in a regio- and diastereoselective manner to provide taxadiene-4(5)-epoxide (12) as a single diastereoisomer, and that this epoxide can be rearranged to give taxa-4(20),11(12)-dien-5α-ol (4). Furthermore, the epoxide 12 rearranges under acidic conditions to give taxa-4(20),11(12)-dien-5α-ol (4), the known bridged ether OCT (5) and the new oxacyclotaxane (OCT2) 15. Contrary to previous speculation, taxadiene-4(5)-epoxide (12) is susceptible to rearrangement when exposed to an iron(III) porphyrin, and these observations justify consideration of epoxide 12 as a chemically competent intermediate on the taxol biosynthetic pathway.
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spelling pubmed-60052632018-07-11 Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway? Barton, Naomi A. Marsh, Benjamin J. Lewis, William Narraidoo, Nathalie Seymour, Graham B. Fray, Rupert Hayes, Christopher J. Chem Sci Chemistry We have shown for the first time that taxadiene (3) can be epoxidised in a regio- and diastereoselective manner to provide taxadiene-4(5)-epoxide (12) as a single diastereoisomer, and that this epoxide can be rearranged to give taxa-4(20),11(12)-dien-5α-ol (4). Furthermore, the epoxide 12 rearranges under acidic conditions to give taxa-4(20),11(12)-dien-5α-ol (4), the known bridged ether OCT (5) and the new oxacyclotaxane (OCT2) 15. Contrary to previous speculation, taxadiene-4(5)-epoxide (12) is susceptible to rearrangement when exposed to an iron(III) porphyrin, and these observations justify consideration of epoxide 12 as a chemically competent intermediate on the taxol biosynthetic pathway. Royal Society of Chemistry 2016-05-01 2016-01-26 /pmc/articles/PMC6005263/ /pubmed/29997802 http://dx.doi.org/10.1039/c5sc03463a Text en This journal is © The Royal Society of Chemistry 2016 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)
spellingShingle Chemistry
Barton, Naomi A.
Marsh, Benjamin J.
Lewis, William
Narraidoo, Nathalie
Seymour, Graham B.
Fray, Rupert
Hayes, Christopher J.
Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title_full Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title_fullStr Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title_full_unstemmed Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title_short Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
title_sort accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6005263/
https://www.ncbi.nlm.nih.gov/pubmed/29997802
http://dx.doi.org/10.1039/c5sc03463a
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