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 rear...
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| Veröffentlicht in: | Chemical science (Cambridge) 2016-01, Vol.7 (5), p.312-317 |
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| creator | Barton, Naomi A Marsh, Benjamin J Lewis, William Narraidoo, Nathalie Seymour, Graham B Fray, Rupert Hayes, Christopher J |
| 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.
We report the first synthesis of taxadiene-4(5)-epoxide, which rearranges upon acid treatment to produce products of relevance to taxol biosynthesis. |
| doi_str_mv | 10.1039/c5sc03463a |
| format | Article |
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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.
We report the first synthesis of taxadiene-4(5)-epoxide, which rearranges upon acid treatment to produce products of relevance to taxol biosynthesis.</description><identifier>ISSN: 2041-6520</identifier><identifier>EISSN: 2041-6539</identifier><identifier>DOI: 10.1039/c5sc03463a</identifier><identifier>PMID: 29997802</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Chemistry ; Ethers ; Exposure ; Pathways ; Porphyrins ; Taxane ; Taxol</subject><ispartof>Chemical science (Cambridge), 2016-01, Vol.7 (5), p.312-317</ispartof><rights>This journal is © The Royal Society of Chemistry 2016 2016</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c474t-87106b6a5072e80c4be51da389381e0a4b6f1ac61d5b2cd3fc38baa00efb6c103</citedby><cites>FETCH-LOGICAL-c474t-87106b6a5072e80c4be51da389381e0a4b6f1ac61d5b2cd3fc38baa00efb6c103</cites><orcidid>0000-0003-1692-3646</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6005263/pdf/$$EPDF$$P50$$Gpubmedcentral$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://www.ncbi.nlm.nih.gov/pmc/articles/PMC6005263/$$EHTML$$P50$$Gpubmedcentral$$Hfree_for_read</linktohtml><link.rule.ids>230,314,723,776,780,860,881,27903,27904,53769,53771</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29997802$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Barton, Naomi A</creatorcontrib><creatorcontrib>Marsh, Benjamin J</creatorcontrib><creatorcontrib>Lewis, William</creatorcontrib><creatorcontrib>Narraidoo, Nathalie</creatorcontrib><creatorcontrib>Seymour, Graham B</creatorcontrib><creatorcontrib>Fray, Rupert</creatorcontrib><creatorcontrib>Hayes, Christopher J</creatorcontrib><title>Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?</title><title>Chemical science (Cambridge)</title><addtitle>Chem Sci</addtitle><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.
We report the first synthesis of taxadiene-4(5)-epoxide, which rearranges upon acid treatment to produce products of relevance to taxol biosynthesis.</description><subject>Chemistry</subject><subject>Ethers</subject><subject>Exposure</subject><subject>Pathways</subject><subject>Porphyrins</subject><subject>Taxane</subject><subject>Taxol</subject><issn>2041-6520</issn><issn>2041-6539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkkFv1DAQhS1URKvSC3eqHEulwNiOHaeHotWqLUiVOABna-JMukbZeIm9tPvvcXfLFk74MjOaT0_2e2bsDYf3HGTzwanoQFZa4gt2JKDipVayOdj3Ag7ZSYw_IB8puRL1K3YomqapDYgj5mbOUYx-vCuGcF-GB99h8mEsYsJERcIHHCleFD5u-87TSGV1pt6VtHqEqchsWmzJMBStD3Ez5jl5V6wwLe5x8_E1e9njEOnkqR6z79dX3-afytsvN5_ns9vSVXWVSlNz0K1GBbUgA65qSfEOpWmk4QRYtbrn6DTvVCtcJ3snTYsIQH2rXTbjmF3udFfrdkmdozFNONjV5Jc4bWxAb__djH5h78IvqwGU0DILnD0JTOHnmmKySx8dDUP2IKyjFaBNI6RW8F-UGzCQ3Vcqo-c71E0hxon6_Y042McM7Vx9nW8znGX49O837NE_iWXg7Q6Yottvnz-B_A2YI6IP</recordid><startdate>20160101</startdate><enddate>20160101</enddate><creator>Barton, Naomi A</creator><creator>Marsh, Benjamin J</creator><creator>Lewis, William</creator><creator>Narraidoo, Nathalie</creator><creator>Seymour, Graham B</creator><creator>Fray, Rupert</creator><creator>Hayes, Christopher J</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>7X8</scope><scope>5PM</scope><orcidid>https://orcid.org/0000-0003-1692-3646</orcidid></search><sort><creationdate>20160101</creationdate><title>Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?</title><author>Barton, Naomi A ; Marsh, Benjamin J ; Lewis, William ; Narraidoo, Nathalie ; Seymour, Graham B ; Fray, Rupert ; Hayes, Christopher J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c474t-87106b6a5072e80c4be51da389381e0a4b6f1ac61d5b2cd3fc38baa00efb6c103</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Chemistry</topic><topic>Ethers</topic><topic>Exposure</topic><topic>Pathways</topic><topic>Porphyrins</topic><topic>Taxane</topic><topic>Taxol</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Barton, Naomi A</creatorcontrib><creatorcontrib>Marsh, Benjamin J</creatorcontrib><creatorcontrib>Lewis, William</creatorcontrib><creatorcontrib>Narraidoo, Nathalie</creatorcontrib><creatorcontrib>Seymour, Graham B</creatorcontrib><creatorcontrib>Fray, Rupert</creatorcontrib><creatorcontrib>Hayes, Christopher J</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>MEDLINE - Academic</collection><collection>PubMed Central (Full Participant titles)</collection><jtitle>Chemical science (Cambridge)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Barton, Naomi A</au><au>Marsh, Benjamin J</au><au>Lewis, William</au><au>Narraidoo, Nathalie</au><au>Seymour, Graham B</au><au>Fray, Rupert</au><au>Hayes, Christopher J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway?</atitle><jtitle>Chemical science (Cambridge)</jtitle><addtitle>Chem Sci</addtitle><date>2016-01-01</date><risdate>2016</risdate><volume>7</volume><issue>5</issue><spage>312</spage><epage>317</epage><pages>312-317</pages><issn>2041-6520</issn><eissn>2041-6539</eissn><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 iron
III
porphyrin, and these observations justify consideration of epoxide
12
as a chemically competent intermediate on the taxol biosynthetic pathway.
We report the first synthesis of taxadiene-4(5)-epoxide, which rearranges upon acid treatment to produce products of relevance to taxol biosynthesis.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>29997802</pmid><doi>10.1039/c5sc03463a</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0003-1692-3646</orcidid><oa>free_for_read</oa></addata></record> |
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| source | DOAJ Directory of Open Access Journals; PubMed Central Open Access; EZB-FREE-00999 freely available EZB journals; PubMed Central |
| subjects | Chemistry Ethers Exposure Pathways Porphyrins Taxane Taxol |
| title | Accessing low-oxidation state taxanes: is taxadiene-4(5)-epoxide on the taxol biosynthetic pathway? |
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