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.

Abstract

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.

Citation

Barton, N. A., Marsh, B. J., Lewis, W., Narraidoo, N., Seymour, G. B., Fray, R. G., & Hayes, C. J. (in press). Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?. Chemical Science, 7(5), https://doi.org/10.1039/c5sc03463a

• Journal Article Type: Article
• Acceptance Date: Jan 26, 2016
• Online Publication Date: Jan 26, 2016
• Deposit Date: Oct 10, 2016
• Publicly Available Date: Oct 10, 2016
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 7
• Issue: 5
• DOI: https://doi.org/10.1039/c5sc03463a
• Public URL: https://nottingham-repository.worktribe.com/output/771607
• Publisher URL: http://pubs.rsc.org/en/Content/ArticleLanding/2016/SC/C5SC03463A#
• Contract Date: Oct 10, 2016