获取低氧化态紫杉烷：紫杉二烯-4(5)-环氧化合物是否处于紫杉醇生物合成途径中？
Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?
作者信息
Barton Naomi A, Marsh Benjamin J, Lewis William, Narraidoo Nathalie, Seymour Graham B, Fray Rupert, Hayes Christopher J
机构信息
School of Chemistry , University of Nottingham , University Park , NG7 2RD , Nottingham , UK.
Division of Plant and Crop Sciences , School of Biosciences , University of Nottingham , Sutton Bonnington , LE12 5RD , Loughborough , UK . Email:
出版信息
Chem Sci. 2016 May 1;7(5):3102-3107. doi: 10.1039/c5sc03463a. Epub 2016 Jan 26.
We have shown for the first time that taxadiene () can be epoxidised in a regio- and diastereoselective manner to provide taxadiene-4(5)-epoxide () as a single diastereoisomer, and that this epoxide can be rearranged to give taxa-4(20),11(12)-dien-5α-ol (). Furthermore, the epoxide rearranges under acidic conditions to give taxa-4(20),11(12)-dien-5α-ol (), the known bridged ether OCT () and the new oxacyclotaxane (OCT2) . Contrary to previous speculation, taxadiene-4(5)-epoxide () is susceptible to rearrangement when exposed to an iron porphyrin, and these observations justify consideration of epoxide as a chemically competent intermediate on the taxol biosynthetic pathway.
我们首次表明，紫杉二烯（）能够以区域和非对映选择性的方式进行环氧化反应，生成作为单一非对映异构体的4(5)-环氧紫杉二烯（），并且该环氧化物能够重排生成4(20),11(12)-二烯-5α-醇紫杉烷（）。此外，环氧化物在酸性条件下重排生成4(20),11(12)-二烯-5α-醇紫杉烷（）、已知的桥连醚OCT（）和新的氧杂环紫杉烷（OCT2）。与之前的推测相反，4(5)-环氧紫杉二烯（）在暴露于铁卟啉时易于重排，这些观察结果证明将环氧化物视为紫杉醇生物合成途径上具有化学活性的中间体是合理的。
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