Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid
A sequential process via photoredox catalysis and Lewis acid mediation for C−F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylati...
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| Veröffentlicht in: | Angewandte Chemie 2024-04, Vol.136 (14), p.n/a |
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| creator | Sugihara, Naoki Nishimoto, Yoshihiro Osakada, Yasuko Fujitsuka, Mamoru Abe, Manabu Yasuda, Makoto |
| description | A sequential process via photoredox catalysis and Lewis acid mediation for C−F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation.
The sequential defluorinative transformation of a difluoromethylene (CF2) unit in perfluoroalkyl compounds has been achieved by a combination of photoredox catalysis and Lewis acid activation. A newly developed phenothiazine‐based catalyst served as an efficient catalyst for defluoroaminoxylation. Spectroscopic measurements revealed the reaction mechanism. AlCl3 facilitated further defluorinative transformation of the aminoxylated compounds. |
| doi_str_mv | 10.1002/ange.202401117 |
| format | Article |
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The sequential defluorinative transformation of a difluoromethylene (CF2) unit in perfluoroalkyl compounds has been achieved by a combination of photoredox catalysis and Lewis acid activation. A newly developed phenothiazine‐based catalyst served as an efficient catalyst for defluoroaminoxylation. Spectroscopic measurements revealed the reaction mechanism. AlCl3 facilitated further defluorinative transformation of the aminoxylated compounds.</description><identifier>ISSN: 0044-8249</identifier><identifier>EISSN: 1521-3757</identifier><identifier>DOI: 10.1002/ange.202401117</identifier><language>eng</language><publisher>Weinheim: Wiley Subscription Services, Inc</publisher><subject>Absorption spectroscopy ; Alcohols ; Aluminum chloride ; Catalysis ; Catalysts ; Fluorine ; Irradiation ; Lewis acid ; Light irradiation ; Perfluoro compounds ; Perfluoroalkyl & polyfluoroalkyl substances ; Phenothiazine ; Photocatalysis ; Photochemistry ; Photoredox catalysis ; Radical ions ; Radical reactions ; Reagents</subject><ispartof>Angewandte Chemie, 2024-04, Vol.136 (14), p.n/a</ispartof><rights>2024 The Authors. Angewandte Chemie published by Wiley-VCH GmbH</rights><rights>2024. This article is published under http://creativecommons.org/licenses/by-nc-nd/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c1177-c7ec983c3e4554317d4cd73442efc0f79a8954f5a0b2cfeae49b76d6c19479e03</cites><orcidid>0000-0002-7182-0503 ; 0000-0003-4078-0112 ; 0000-0002-2013-4394 ; 0000-0002-6618-2893 ; 0000-0002-5778-5369 ; 0000-0002-2336-4355</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.202401117$$EPDF$$P50$$Gwiley$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fange.202401117$$EHTML$$P50$$Gwiley$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids></links><search><creatorcontrib>Sugihara, Naoki</creatorcontrib><creatorcontrib>Nishimoto, Yoshihiro</creatorcontrib><creatorcontrib>Osakada, Yasuko</creatorcontrib><creatorcontrib>Fujitsuka, Mamoru</creatorcontrib><creatorcontrib>Abe, Manabu</creatorcontrib><creatorcontrib>Yasuda, Makoto</creatorcontrib><title>Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid</title><title>Angewandte Chemie</title><description>A sequential process via photoredox catalysis and Lewis acid mediation for C−F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation.
The sequential defluorinative transformation of a difluoromethylene (CF2) unit in perfluoroalkyl compounds has been achieved by a combination of photoredox catalysis and Lewis acid activation. A newly developed phenothiazine‐based catalyst served as an efficient catalyst for defluoroaminoxylation. Spectroscopic measurements revealed the reaction mechanism. AlCl3 facilitated further defluorinative transformation of the aminoxylated compounds.</description><subject>Absorption spectroscopy</subject><subject>Alcohols</subject><subject>Aluminum chloride</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Fluorine</subject><subject>Irradiation</subject><subject>Lewis acid</subject><subject>Light irradiation</subject><subject>Perfluoro compounds</subject><subject>Perfluoroalkyl & polyfluoroalkyl substances</subject><subject>Phenothiazine</subject><subject>Photocatalysis</subject><subject>Photochemistry</subject><subject>Photoredox catalysis</subject><subject>Radical ions</subject><subject>Radical reactions</subject><subject>Reagents</subject><issn>0044-8249</issn><issn>1521-3757</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>24P</sourceid><sourceid>WIN</sourceid><recordid>eNqFUU1PGzEQtSqQGqDXni1x3tT2euOYW7okoVIEkZqcV4533Jhu7NT2ii4njhwRf6P_il_SRang2NNoZt578_EQ-kzJkBLCvij3A4aMME4opeIDGtCC0SwXhThCA0I4z8aMy4_oJMZbQsiICTlAf77DrxZcsqrB5cvj8wx_9a7Gq6BcND7sVLLeYW9w2gK-tKZpffA7SNuuAQd47WzC1uElhENLNT-7Bs-Db_fxAk9w6Xcb695UZtbBy8PTqnVQ4-UWnE9bq-77ap_55APU_jcuVVJNFxNW_SoLuLMRT7Stz9CxUU2ET__iKVrPpqvyKlvczL-Vk0Wm-7tFpgVoOc51DrwoeE5FzXUtcs4ZGE2MkGosC24KRTZMG1DA5UaM6pGmkgsJJD9F5wfdffD9c2Kqbn0bXD-yYlLkOS-EYD1qeEDp4GMMYKp9sDsVuoqS6tWQ6tWQ6s2QniAPhDvbQPcfdDW5nk_fuX8BLeOUeQ</recordid><startdate>20240402</startdate><enddate>20240402</enddate><creator>Sugihara, Naoki</creator><creator>Nishimoto, Yoshihiro</creator><creator>Osakada, Yasuko</creator><creator>Fujitsuka, Mamoru</creator><creator>Abe, Manabu</creator><creator>Yasuda, Makoto</creator><general>Wiley Subscription Services, Inc</general><scope>24P</scope><scope>WIN</scope><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/0000-0002-7182-0503</orcidid><orcidid>https://orcid.org/0000-0003-4078-0112</orcidid><orcidid>https://orcid.org/0000-0002-2013-4394</orcidid><orcidid>https://orcid.org/0000-0002-6618-2893</orcidid><orcidid>https://orcid.org/0000-0002-5778-5369</orcidid><orcidid>https://orcid.org/0000-0002-2336-4355</orcidid></search><sort><creationdate>20240402</creationdate><title>Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid</title><author>Sugihara, Naoki ; Nishimoto, Yoshihiro ; Osakada, Yasuko ; Fujitsuka, Mamoru ; Abe, Manabu ; Yasuda, Makoto</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1177-c7ec983c3e4554317d4cd73442efc0f79a8954f5a0b2cfeae49b76d6c19479e03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Absorption spectroscopy</topic><topic>Alcohols</topic><topic>Aluminum chloride</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Fluorine</topic><topic>Irradiation</topic><topic>Lewis acid</topic><topic>Light irradiation</topic><topic>Perfluoro compounds</topic><topic>Perfluoroalkyl & polyfluoroalkyl substances</topic><topic>Phenothiazine</topic><topic>Photocatalysis</topic><topic>Photochemistry</topic><topic>Photoredox catalysis</topic><topic>Radical ions</topic><topic>Radical reactions</topic><topic>Reagents</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Sugihara, Naoki</creatorcontrib><creatorcontrib>Nishimoto, Yoshihiro</creatorcontrib><creatorcontrib>Osakada, Yasuko</creatorcontrib><creatorcontrib>Fujitsuka, Mamoru</creatorcontrib><creatorcontrib>Abe, Manabu</creatorcontrib><creatorcontrib>Yasuda, Makoto</creatorcontrib><collection>Wiley Online Library Open Access</collection><collection>Wiley Free Content</collection><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>Sugihara, Naoki</au><au>Nishimoto, Yoshihiro</au><au>Osakada, Yasuko</au><au>Fujitsuka, Mamoru</au><au>Abe, Manabu</au><au>Yasuda, Makoto</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid</atitle><jtitle>Angewandte Chemie</jtitle><date>2024-04-02</date><risdate>2024</risdate><volume>136</volume><issue>14</issue><epage>n/a</epage><issn>0044-8249</issn><eissn>1521-3757</eissn><abstract>A sequential process via photoredox catalysis and Lewis acid mediation for C−F bond transformation of the CF2 unit in perfluoroalkyl groups has been achieved to transform perfluoroalkylarenes into complex fluoroalkylated compounds. A phenothiazine‐based photocatalyst promotes the defluoroaminoxylation of perfluoroalkylarenes with (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) under visible light irradiation, affording the corresponding aminoxylated products. These products undergo a further defluorinative transformation with various organosilicon reagents mediated by AlCl3 to provide highly functionalized perfluoroalkyl alcohols. Our novel phenothiazine catalyst works efficiently in the defluoroaminoxylation. Transient absorption spectroscopy revealed that the catalyst regeneration step is crucial for the photocatalytic aminoxylation.
The sequential defluorinative transformation of a difluoromethylene (CF2) unit in perfluoroalkyl compounds has been achieved by a combination of photoredox catalysis and Lewis acid activation. A newly developed phenothiazine‐based catalyst served as an efficient catalyst for defluoroaminoxylation. Spectroscopic measurements revealed the reaction mechanism. AlCl3 facilitated further defluorinative transformation of the aminoxylated compounds.</abstract><cop>Weinheim</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/ange.202401117</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-7182-0503</orcidid><orcidid>https://orcid.org/0000-0003-4078-0112</orcidid><orcidid>https://orcid.org/0000-0002-2013-4394</orcidid><orcidid>https://orcid.org/0000-0002-6618-2893</orcidid><orcidid>https://orcid.org/0000-0002-5778-5369</orcidid><orcidid>https://orcid.org/0000-0002-2336-4355</orcidid><oa>free_for_read</oa></addata></record> |
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| subjects | Absorption spectroscopy Alcohols Aluminum chloride Catalysis Catalysts Fluorine Irradiation Lewis acid Light irradiation Perfluoro compounds Perfluoroalkyl & polyfluoroalkyl substances Phenothiazine Photocatalysis Photochemistry Photoredox catalysis Radical ions Radical reactions Reagents |
| title | Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid |
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