Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols
Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatro...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie 2018-10, Vol.130 (43), p.14426-14430 |
|---|---|
| Hauptverfasser: | , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 14430 |
|---|---|
| container_issue | 43 |
| container_start_page | 14426 |
| container_title | Angewandte Chemie |
| container_volume | 130 |
| creator | Okamoto, Koichi Hori, Mitsuki Yanagi, Tomoyuki Murakami, Kei Nogi, Keisuke Yorimitsu, Hideki |
| description | Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatropic rearrangement, (2) Zn‐mediated smooth reductive removal of fluoride from the dearomatized intermediate, and (3) acid‐promoted cyclization/aromatization. Mechanistic investigations revealed important characteristic reactivity of polyfluorophenols in the present system. Some of the fluorinated benzofuran products were transformed by utilizing the 2‐methylsulfanyl moieties.
Einfach synthetisiert werden fluorierte Benzofurane ausgehend von Polyfluorphenolen. Die verwendete Desaromatisierungs‐Defluorierungs‐Strategie beruht auf drei Prozessen: einer unvollständigen Pummerer‐Reaktion mit nachfolgender sigmatroper [3,3]‐Umlagerung, Zn‐vermittelter Defluorierung der desaromatisierten Zwischenstufe unter milden Bedingungen und säureunterstützter Cyclisierung samt Aromatisierung. |
| doi_str_mv | 10.1002/ange.201809035 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2120119848</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2120119848</sourcerecordid><originalsourceid>FETCH-LOGICAL-c2285-bd6e1b055dc4e79f15474ac3ca3ade2cd2f7eec00e0ab34855d6cf51ec1928823</originalsourceid><addsrcrecordid>eNqFkM1OAjEUhRujiYhuXTdxPdB2OsyMO0RAE6Im4HpSOrcwZGixnYkZnkC3PqJPYgF_li5ubk7ynXOSg9AlJR1KCOsKvYAOIzQhKQmjI9SiEaNBGEfxMWoRwnmQMJ6eojPnVoSQHovTFnqfFou1qKzZFBLfgrDGq2Lrz-juLaiyNrbQe4mnlRUVLBqsjMWDz7ePEZ5ZoZ2X6z1xjaeNrpbgCoeNwqMfM-T4BvTWqHqHY-VL8JMpm3262SxBm9KdoxMlSgcX37-NnkfD2eAumDyO7wf9SSAZS6JgnveAzkkU5ZJDnCoa8ZgLGUoRihyYzJmKASQhQMQ85IkHe1JFFCRNWZKwsI2uDrkba15qcFW2MrXVvjJj1M9H04QnnuocKGmNcxZUtrHFWtgmoyTbzZ3t5s5-5_aG9GB4LUpo_qGz_sN4-Of9Aiq0ibI</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2120119848</pqid></control><display><type>article</type><title>Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols</title><source>Wiley Journals</source><creator>Okamoto, Koichi ; Hori, Mitsuki ; Yanagi, Tomoyuki ; Murakami, Kei ; Nogi, Keisuke ; Yorimitsu, Hideki</creator><creatorcontrib>Okamoto, Koichi ; Hori, Mitsuki ; Yanagi, Tomoyuki ; Murakami, Kei ; Nogi, Keisuke ; Yorimitsu, Hideki</creatorcontrib><description>Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatropic rearrangement, (2) Zn‐mediated smooth reductive removal of fluoride from the dearomatized intermediate, and (3) acid‐promoted cyclization/aromatization. Mechanistic investigations revealed important characteristic reactivity of polyfluorophenols in the present system. Some of the fluorinated benzofuran products were transformed by utilizing the 2‐methylsulfanyl moieties.
Einfach synthetisiert werden fluorierte Benzofurane ausgehend von Polyfluorphenolen. Die verwendete Desaromatisierungs‐Defluorierungs‐Strategie beruht auf drei Prozessen: einer unvollständigen Pummerer‐Reaktion mit nachfolgender sigmatroper [3,3]‐Umlagerung, Zn‐vermittelter Defluorierung der desaromatisierten Zwischenstufe unter milden Bedingungen und säureunterstützter Cyclisierung samt Aromatisierung.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.201809035</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Benzofuran ; Benzofurane ; Chemistry ; Defluorierende Umwandlungen ; Defluorination ; Fluorarene ; Fluorides ; Fluorination ; Pummerer-Reaktion ; Sigmatrope Desaromatisierung ; Synthesis ; Zinc</subject><ispartof>Angewandte Chemie, 2018-10, Vol.130 (43), p.14426-14430</ispartof><rights>2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2285-bd6e1b055dc4e79f15474ac3ca3ade2cd2f7eec00e0ab34855d6cf51ec1928823</citedby><cites>FETCH-LOGICAL-c2285-bd6e1b055dc4e79f15474ac3ca3ade2cd2f7eec00e0ab34855d6cf51ec1928823</cites><orcidid>0000-0002-0153-1888 ; 0000-0001-8478-1227</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fange.201809035$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fange.201809035$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids></links><search><creatorcontrib>Okamoto, Koichi</creatorcontrib><creatorcontrib>Hori, Mitsuki</creatorcontrib><creatorcontrib>Yanagi, Tomoyuki</creatorcontrib><creatorcontrib>Murakami, Kei</creatorcontrib><creatorcontrib>Nogi, Keisuke</creatorcontrib><creatorcontrib>Yorimitsu, Hideki</creatorcontrib><title>Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols</title><title>Angewandte Chemie</title><description>Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatropic rearrangement, (2) Zn‐mediated smooth reductive removal of fluoride from the dearomatized intermediate, and (3) acid‐promoted cyclization/aromatization. Mechanistic investigations revealed important characteristic reactivity of polyfluorophenols in the present system. Some of the fluorinated benzofuran products were transformed by utilizing the 2‐methylsulfanyl moieties.
Einfach synthetisiert werden fluorierte Benzofurane ausgehend von Polyfluorphenolen. Die verwendete Desaromatisierungs‐Defluorierungs‐Strategie beruht auf drei Prozessen: einer unvollständigen Pummerer‐Reaktion mit nachfolgender sigmatroper [3,3]‐Umlagerung, Zn‐vermittelter Defluorierung der desaromatisierten Zwischenstufe unter milden Bedingungen und säureunterstützter Cyclisierung samt Aromatisierung.</description><subject>Benzofuran</subject><subject>Benzofurane</subject><subject>Chemistry</subject><subject>Defluorierende Umwandlungen</subject><subject>Defluorination</subject><subject>Fluorarene</subject><subject>Fluorides</subject><subject>Fluorination</subject><subject>Pummerer-Reaktion</subject><subject>Sigmatrope Desaromatisierung</subject><subject>Synthesis</subject><subject>Zinc</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNqFkM1OAjEUhRujiYhuXTdxPdB2OsyMO0RAE6Im4HpSOrcwZGixnYkZnkC3PqJPYgF_li5ubk7ynXOSg9AlJR1KCOsKvYAOIzQhKQmjI9SiEaNBGEfxMWoRwnmQMJ6eojPnVoSQHovTFnqfFou1qKzZFBLfgrDGq2Lrz-juLaiyNrbQe4mnlRUVLBqsjMWDz7ePEZ5ZoZ2X6z1xjaeNrpbgCoeNwqMfM-T4BvTWqHqHY-VL8JMpm3262SxBm9KdoxMlSgcX37-NnkfD2eAumDyO7wf9SSAZS6JgnveAzkkU5ZJDnCoa8ZgLGUoRihyYzJmKASQhQMQ85IkHe1JFFCRNWZKwsI2uDrkba15qcFW2MrXVvjJj1M9H04QnnuocKGmNcxZUtrHFWtgmoyTbzZ3t5s5-5_aG9GB4LUpo_qGz_sN4-Of9Aiq0ibI</recordid><startdate>20181022</startdate><enddate>20181022</enddate><creator>Okamoto, Koichi</creator><creator>Hori, Mitsuki</creator><creator>Yanagi, Tomoyuki</creator><creator>Murakami, Kei</creator><creator>Nogi, Keisuke</creator><creator>Yorimitsu, Hideki</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0002-0153-1888</orcidid><orcidid>https://orcid.org/0000-0001-8478-1227</orcidid></search><sort><creationdate>20181022</creationdate><title>Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols</title><author>Okamoto, Koichi ; Hori, Mitsuki ; Yanagi, Tomoyuki ; Murakami, Kei ; Nogi, Keisuke ; Yorimitsu, Hideki</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2285-bd6e1b055dc4e79f15474ac3ca3ade2cd2f7eec00e0ab34855d6cf51ec1928823</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Benzofuran</topic><topic>Benzofurane</topic><topic>Chemistry</topic><topic>Defluorierende Umwandlungen</topic><topic>Defluorination</topic><topic>Fluorarene</topic><topic>Fluorides</topic><topic>Fluorination</topic><topic>Pummerer-Reaktion</topic><topic>Sigmatrope Desaromatisierung</topic><topic>Synthesis</topic><topic>Zinc</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Okamoto, Koichi</creatorcontrib><creatorcontrib>Hori, Mitsuki</creatorcontrib><creatorcontrib>Yanagi, Tomoyuki</creatorcontrib><creatorcontrib>Murakami, Kei</creatorcontrib><creatorcontrib>Nogi, Keisuke</creatorcontrib><creatorcontrib>Yorimitsu, Hideki</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Angewandte Chemie</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Okamoto, Koichi</au><au>Hori, Mitsuki</au><au>Yanagi, Tomoyuki</au><au>Murakami, Kei</au><au>Nogi, Keisuke</au><au>Yorimitsu, Hideki</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols</atitle><jtitle>Angewandte Chemie</jtitle><date>2018-10-22</date><risdate>2018</risdate><volume>130</volume><issue>43</issue><spage>14426</spage><epage>14430</epage><pages>14426-14430</pages><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>Facile synthesis of fluorinated benzofurans from polyfluorophenols has been accomplished by means of a sigmatropic dearomatization/defluorination strategy composed of three processes: (1) interrupted Pummerer reaction of ketene dithioacetal monoxides with polyfluorophenols followed by [3,3] sigmatropic rearrangement, (2) Zn‐mediated smooth reductive removal of fluoride from the dearomatized intermediate, and (3) acid‐promoted cyclization/aromatization. Mechanistic investigations revealed important characteristic reactivity of polyfluorophenols in the present system. Some of the fluorinated benzofuran products were transformed by utilizing the 2‐methylsulfanyl moieties.
Einfach synthetisiert werden fluorierte Benzofurane ausgehend von Polyfluorphenolen. Die verwendete Desaromatisierungs‐Defluorierungs‐Strategie beruht auf drei Prozessen: einer unvollständigen Pummerer‐Reaktion mit nachfolgender sigmatroper [3,3]‐Umlagerung, Zn‐vermittelter Defluorierung der desaromatisierten Zwischenstufe unter milden Bedingungen und säureunterstützter Cyclisierung samt Aromatisierung.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.201809035</doi><tpages>5</tpages><orcidid>https://orcid.org/0000-0002-0153-1888</orcidid><orcidid>https://orcid.org/0000-0001-8478-1227</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0044-8249 |
| ispartof | Angewandte Chemie, 2018-10, Vol.130 (43), p.14426-14430 |
| issn | 0044-8249 1521-3757 |
| language | eng |
| recordid | cdi_proquest_journals_2120119848 |
| source | Wiley Journals |
| subjects | Benzofuran Benzofurane Chemistry Defluorierende Umwandlungen Defluorination Fluorarene Fluorides Fluorination Pummerer-Reaktion Sigmatrope Desaromatisierung Synthesis Zinc |
| title | Sigmatropic Dearomatization/Defluorination Strategy for C−F Transformation: Synthesis of Fluorinated Benzofurans from Polyfluorophenols |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-05T13%3A26%3A38IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Sigmatropic%20Dearomatization/Defluorination%20Strategy%20for%20C%E2%88%92F%20Transformation:%20Synthesis%20of%20Fluorinated%20Benzofurans%20from%20Polyfluorophenols&rft.jtitle=Angewandte%20Chemie&rft.au=Okamoto,%20Koichi&rft.date=2018-10-22&rft.volume=130&rft.issue=43&rft.spage=14426&rft.epage=14430&rft.pages=14426-14430&rft.issn=0044-8249&rft.eissn=1521-3757&rft_id=info:doi/10.1002/ange.201809035&rft_dat=%3Cproquest_cross%3E2120119848%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2120119848&rft_id=info:pmid/&rfr_iscdi=true |