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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| Format: | Article |
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Royal Society of Chemistry
2016
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| Online Access: | https://eprints.nottingham.ac.uk/37455/ |
| _version_ | 1848795461821923328 |
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| author | Barton, Naomi A. Marsh, Benjamin J. Lewis, William Narraidoo, Nathalie Seymour, Graham B. Fray, Rupert George Hayes, Christopher J. |
| author_facet | Barton, Naomi A. Marsh, Benjamin J. Lewis, William Narraidoo, Nathalie Seymour, Graham B. Fray, Rupert George Hayes, Christopher J. |
| author_sort | Barton, Naomi A. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| 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 ironIII porphyrin, and these observations justify consideration of epoxide 12 as a chemically competent intermediate on the taxol biosynthetic pathway. |
| first_indexed | 2025-11-14T19:32:28Z |
| format | Article |
| id | nottingham-37455 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:32:28Z |
| publishDate | 2016 |
| publisher | Royal Society of Chemistry |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-374552020-05-04T17:30:01Z https://eprints.nottingham.ac.uk/37455/ 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 George Hayes, Christopher J. 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 ironIII porphyrin, and these observations justify consideration of epoxide 12 as a chemically competent intermediate on the taxol biosynthetic pathway. Royal Society of Chemistry 2016-01-26 Article PeerReviewed Barton, Naomi A., Marsh, Benjamin J., Lewis, William, Narraidoo, Nathalie, Seymour, Graham B., Fray, Rupert George and Hayes, Christopher J. (2016) Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway? Chemical Science, 7 (5). pp. 3102-3107. ISSN 2041-6539 http://pubs.rsc.org/en/Content/ArticleLanding/2016/SC/C5SC03463A# doi:10.1039/c5sc03463a doi:10.1039/c5sc03463a |
| spellingShingle | Barton, Naomi A. Marsh, Benjamin J. Lewis, William Narraidoo, Nathalie Seymour, Graham B. Fray, Rupert George 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? |
| url | https://eprints.nottingham.ac.uk/37455/ https://eprints.nottingham.ac.uk/37455/ https://eprints.nottingham.ac.uk/37455/ |