Accessing low-oxidation state taxanes: is taxadiene 4(5)-epoxide on the taxol biosynthetic pathway
Barton, Naomi A. and Marsh, Benjamin J. and Narraidoo, Nathalie and Seymour, Graham B. and 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 . pp. 3102-3107. ISSN 2041-6539
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.
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