15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study
A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as...
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| Veröffentlicht in: | Journal of organic chemistry 2018-05, Vol.83 (10), p.5480-5495 |
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| container_title | Journal of organic chemistry |
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| creator | Álvarez-Calero, José María Ruiz, Enrique López-Pérez, José Luis Jaraíz, Martín Rubio, José E Jorge, Zacarías D Suárez, Margarita Massanet, Guillermo M |
| description | A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken. |
| doi_str_mv | 10.1021/acs.joc.8b00407 |
| format | Article |
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Experimental and DFT Study</title><source>American Chemical Society Journals</source><creator>Álvarez-Calero, José María ; Ruiz, Enrique ; López-Pérez, José Luis ; Jaraíz, Martín ; Rubio, José E ; Jorge, Zacarías D ; Suárez, Margarita ; Massanet, Guillermo M</creator><creatorcontrib>Álvarez-Calero, José María ; Ruiz, Enrique ; López-Pérez, José Luis ; Jaraíz, Martín ; Rubio, José E ; Jorge, Zacarías D ; Suárez, Margarita ; Massanet, Guillermo M</creatorcontrib><description>A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken.</description><identifier>ISSN: 0022-3263</identifier><identifier>ISSN: 1520-6904</identifier><identifier>EISSN: 1520-6904</identifier><identifier>DOI: 10.1021/acs.joc.8b00407</identifier><identifier>PMID: 29694044</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>acetone ; artemisinin ; biomimetics ; catalysts ; chemical structure ; cyclization reactions ; eudesmanolides ; guaianolides ; Lewis acids ; organic chemistry ; solvents</subject><ispartof>Journal of organic chemistry, 2018-05, Vol.83 (10), p.5480-5495</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a366t-e465f4507eee1086d93cb12c195a681fce38f9075b5bae22e8274c0630396f333</citedby><cites>FETCH-LOGICAL-a366t-e465f4507eee1086d93cb12c195a681fce38f9075b5bae22e8274c0630396f333</cites><orcidid>0000-0001-6688-3158 ; 0000-0002-7463-5696</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.joc.8b00407$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.joc.8b00407$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/29694044$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Álvarez-Calero, José María</creatorcontrib><creatorcontrib>Ruiz, Enrique</creatorcontrib><creatorcontrib>López-Pérez, José Luis</creatorcontrib><creatorcontrib>Jaraíz, Martín</creatorcontrib><creatorcontrib>Rubio, José E</creatorcontrib><creatorcontrib>Jorge, Zacarías D</creatorcontrib><creatorcontrib>Suárez, Margarita</creatorcontrib><creatorcontrib>Massanet, Guillermo M</creatorcontrib><title>15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study</title><title>Journal of organic chemistry</title><addtitle>J. Org. Chem</addtitle><description>A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken.</description><subject>acetone</subject><subject>artemisinin</subject><subject>biomimetics</subject><subject>catalysts</subject><subject>chemical structure</subject><subject>cyclization reactions</subject><subject>eudesmanolides</subject><subject>guaianolides</subject><subject>Lewis acids</subject><subject>organic chemistry</subject><subject>solvents</subject><issn>0022-3263</issn><issn>1520-6904</issn><issn>1520-6904</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNqFkU9v1DAQxS1E1S6lZ27IRySU7diOnYQb2rYUaSUktpwjx5mUVNl46z9VwyfiY-IoCzdUX-yxf--NPI-QdwzWDDi71MavH6xZlw1ADsUrsmKSQ6YqyF-TFQDnmeBKnJE33j9AWlLKU3LGK1XlkOcr8pvJ7HZqnX2e7tHttXF6tEPfoqfa052NzqSj7eguuGhCdHqgV_0TOt-H6RPdTWP4ib5fEPSPsQ_oDjgi3WoT7JjEzUQ3kxn6Xzr0dqR6bOl31C41usc9jmGuzPzk1_T6-YCun29Tn5m8urlLrWM7vSUnnR48Xhz3c_Lj5vpuc5ttv335uvm8zbRQKmSYK9nlEgpEZFCqthKmYdywSmpVss6gKLsKCtnIRiPnWPIiN6AEiEp1Qohz8mHxPTj7GNGHet97g8OgR7TR15wBE6JK43sZBcFyLoqqSOjlghpnvXfY1Yf0Te2mmkE9J1mnJOuUZH1MMineH81js8f2H_83ugR8XIBFGd2YxvJfuz-aq6vj</recordid><startdate>20180518</startdate><enddate>20180518</enddate><creator>Álvarez-Calero, José María</creator><creator>Ruiz, Enrique</creator><creator>López-Pérez, José Luis</creator><creator>Jaraíz, Martín</creator><creator>Rubio, José E</creator><creator>Jorge, Zacarías D</creator><creator>Suárez, Margarita</creator><creator>Massanet, Guillermo M</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7S9</scope><scope>L.6</scope><orcidid>https://orcid.org/0000-0001-6688-3158</orcidid><orcidid>https://orcid.org/0000-0002-7463-5696</orcidid></search><sort><creationdate>20180518</creationdate><title>15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study</title><author>Álvarez-Calero, José María ; Ruiz, Enrique ; López-Pérez, José Luis ; Jaraíz, Martín ; Rubio, José E ; Jorge, Zacarías D ; Suárez, Margarita ; Massanet, Guillermo M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a366t-e465f4507eee1086d93cb12c195a681fce38f9075b5bae22e8274c0630396f333</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>acetone</topic><topic>artemisinin</topic><topic>biomimetics</topic><topic>catalysts</topic><topic>chemical structure</topic><topic>cyclization reactions</topic><topic>eudesmanolides</topic><topic>guaianolides</topic><topic>Lewis acids</topic><topic>organic chemistry</topic><topic>solvents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Álvarez-Calero, José María</creatorcontrib><creatorcontrib>Ruiz, Enrique</creatorcontrib><creatorcontrib>López-Pérez, José Luis</creatorcontrib><creatorcontrib>Jaraíz, Martín</creatorcontrib><creatorcontrib>Rubio, José E</creatorcontrib><creatorcontrib>Jorge, Zacarías D</creatorcontrib><creatorcontrib>Suárez, Margarita</creatorcontrib><creatorcontrib>Massanet, Guillermo M</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>AGRICOLA</collection><collection>AGRICOLA - Academic</collection><jtitle>Journal of organic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Álvarez-Calero, José María</au><au>Ruiz, Enrique</au><au>López-Pérez, José Luis</au><au>Jaraíz, Martín</au><au>Rubio, José E</au><au>Jorge, Zacarías D</au><au>Suárez, Margarita</au><au>Massanet, Guillermo M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study</atitle><jtitle>Journal of organic chemistry</jtitle><addtitle>J. Org. Chem</addtitle><date>2018-05-18</date><risdate>2018</risdate><volume>83</volume><issue>10</issue><spage>5480</spage><epage>5495</epage><pages>5480-5495</pages><issn>0022-3263</issn><issn>1520-6904</issn><eissn>1520-6904</eissn><abstract>A study on the electrophile-induced rearrangement of two 15-hydroxygermacranolides, salonitenolide and artemisiifolin, was carried out. These compounds underwent electrophilic intramolecular cyclizations or acid-mediated rearrangements to give sesquiterpene lactones with different skeletons such as eudesmanolides, guaianolides, amorphanolides, or other germacranolides. The cyclization that gives guaianolides can be considered a biomimetic route to this type of sesquiterpene lactones. The use of acetone as a solvent changes the reactivity of the two starting germacranolides to the acid catalysts, with a 4,15-diol acetonide being the main product obtained. The δ-amorphenolide obtained by intramolecular cyclization of this acetonide is a valuable intermediate for accessing the antimalarials artemisinin and its derivatives. Mechanistic proposals for the transformations are raised, and to provide support them, quantum chemical calculations [DFT B3LYP/6-31+G(d,p) level] were undertaken.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>29694044</pmid><doi>10.1021/acs.joc.8b00407</doi><tpages>16</tpages><orcidid>https://orcid.org/0000-0001-6688-3158</orcidid><orcidid>https://orcid.org/0000-0002-7463-5696</orcidid></addata></record> |
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| subjects | acetone artemisinin biomimetics catalysts chemical structure cyclization reactions eudesmanolides guaianolides Lewis acids organic chemistry solvents |
| title | 15-Hydroxygermacranolides as Sources of Structural Diversity: Synthesis of Sesquiterpene Lactones by Cyclization and Rearrangement Reactions. Experimental and DFT Study |
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